- For the digital companion comic series, see .
- "It was awesome. I mean it was terrible, but it was awesome."
- —Kara to Clark.
When a new threat emerges in National City, Kara/Supergirl teams up with her cousin, Clark Kent/Superman, to stop it. Kara is thrilled to have family in town but it leaves Alex feeling a bit left out. Meanwhile, Hank and Supergirl are stunned by the pod that came crashing to Earth.
A pod careens through National City. Supergirl and Martian Manhunter pursue. The pod knocks a worker off a building which J'onn handles. They both land at the pod's crash site to find that the pod is identical to Kara's pod and there is a comatose alien inside
Afterwards, J'onn flies Kara to a new D.E.O. headquarters, a skyscraper, to which Kara wonders why J'onn had her fly to the cave headquarters every day. They place the comatose man in the infirmary and believe he is from Krypton due to the pod and the fact that syringe needles were unable to penetrate his skin. J'onn tasks Winn with gathering more information on the pod. Alex asks Kara about her and James Olsen's impending date and notices Kara acting overeager to mask her true feelings.
At CatCo, Cat Grant asks Kara about which job she has decided on. Kara says an online quiz claimed that marketing was her ideal career path, but Cat thought that was pathetic. Cat prods Kara to look inward to find out her purpose. Cat then summons her new assistant, Eve Teschmacher, and chastises her improper salad preparation. Cat told Kara she wasn't thrilled by Kara's choice of her replacement.
James arrives to Kara's apartment and brings her favorites, pizza and potstickers. James asks her about the Venture launch, knowing that Kara is interested and tells her that he's okay with her watching it on TV. They watch the broadcast and see that the Venture is crashing. Meanwhile, Clark Kent is on the phone with Perry White when he sees the Venture malfunction on the news. Kara and Clark race off to save the space shuttle. Supergirl steadies the ship as Superman super-breathes to extinguish the fire. As they land and save the ship, they greet a group of bicyclists.
They arrive back at the D.E.O. building. The various D.E.O. staffers stop what they're doing and look in awe when Superman arrives. Superman shakes hands and Kara introduces him to a nervous Winn. He offers his assistance to Alex in the search for her father and coldly greets J'onn. They all go to the comatose alien's room. Winn figures out that the pod traveled through the Well of Stars where time doesn't pass, explaining the alien's lack of aging. J'onn then tells them that the Venture suffered an explosion while rocketing to space and that they should investigate. Kara and Clark leave, so Alex asks J'onn what happened between him and Clark, but J'onn walks away.
Kara takes Clark to CatCo where Clark and James reunite. Clark then meets Cat Grant, who gushes over him. Cat takes him on a tour of CatCo. Kara apologizes to James about their date being cut short and promises to make it up to him. After getting a call from Alex, Kara tells Clark that Lena Luthor was booked on the Venture but didn't show up to the flight.
Meanwhile, John Corben is meeting with a dealer about a weaponized drone. He kills the dealer with the drone and calls someone on the phone saying that due to Superman and Supergirl's rescue of the Venture, he's changing plans.
Kara and Clark question Lena Luthor about any involvement with the shuttle disaster. Both Kryptonian cousins discreetly x-rays the room, while Lena was looking away, but didn't find anything suspicious. Lena tells them that she wasn't on the shuttle because of her plans to rename her company from Luther Corp to L-Corp and change her company for the better, since she intends to redeem the Luthor name, and also to make a name for herself this way altogether. Clark is skeptical of Lena due to his past involvement with her brother but Kara believes her. Clark then asks Kara about her relationship with James. Kara tells him how she is struggling to balance her life as Kara and as Supergirl but Clark assures her that she will know if James and her are meant to be together.
At the D.E.O., Alex confronted J'onn about Operation: Emerald. J'onn told her that he and Superman investigated a meteorite that contained what J'onn named kryptonite. Superman wanted to destroy the kryptonite but J'onn decided to keep it to fight back against other Kryptonians.
Winn's investigation found that the part that caused the Venture to explode was housed under the same seat Lena Luthor was supposed to sit in, indicating that Lena was the target.
Lena boarded a helicopter. While en route, Corben's attack drones open fire on her helicopter. Supergirl and Superman arrived and shielded the helicopter from the bullets. Corben tells them he has additional drones targeting civilians throughout the city. Clark rescues the civilians while Kara protects the chopper and rescues Lena.
Later, Kara meets up with James. James tells her that he has noticed a change in Kara and she tells him she doesn't know if their relationship is what she wants anymore. Kara talks to Cat who tells her that something is wrong with her because she is afraid of change and encourages Kara to be daring.
Winn analyzes drone and links it to international assassin John Corben. After the briefing, Alex prods J'onn to talk to Clark who adamantly tells him that as long as J'onn keeps kryptonite at the D.E.O., he is unwilling to be a part of their operation.
Lena pushes forward with the renaming ceremony despite Kara encouraging her to cancel it. During her speech, explosions go off. Kara saves James and a lady from falling rubble. Alex pursues Corben who nearly shoots Lena. The Luthor Corp/L-Corp building begins to fall due to the bombs. Clark holds the building while Kara repairs the damaged structure. Alex fights Corben hand to hand but Corben gets the upper-hand and holds Alex at gunpoint in front of Kara. From behind, Lena shoots Corben who is taken to a hospital.
After the attack, Lena thanks Clark for the positive story he published about L-Corp. Clark apologizes to Lena about his initial opinions of her. Lena wishes them well and tells Kara that she hopes it's not the last time they see each other.
At CatCo, Kara tells Cat that she has decided that she wants to work for CatCo as a reporter in order to tell stories that will improve the world and push her out of her comfort zone. Cat shows Kara her résumé with reporter written on it, which Cat had written the day Kara first interviewed for her assistant job. Cat tells her she sees the hero within Kara and wants Kara to make her proud. Kara talks to James admitting that something has changed and tells him that they should stay as friends.
J'onn makes Winn a D.E.O. agent. Clark tells Kara that he's going to stay in town for a little bit hoping to have Kara tell him stories about Krypton and his parents. Alex then alerts them of a robbery so the two of them fly away.
An unknown woman has Corben moved from the hospital. She looks over Corben and offers him a place in Project Cadmus which John accepts. The woman then presses a button causing Corben's body to change, proclaiming "Long live Metallo".
- J'onn claims to have invented the name "Kryptonite", which is unique to this series.
- It is revealed that Clark used to work with the D.E.O., until he had a huge falling out with J'onn regarding the organization keeping Kryptonite as weapons.
- From this episode onwards Calista Flockhart is no longer a series regular. This is due to the show's production team relocating from Los Angeles to Vancouver, Canada, as Flockhart was averse to moving out of LA. Despite this, she continues to be in involved in the show (albeit as a recurring/guest star).
- The episode's title is a reference to The Adventures of Superman comics, as well as , the digital tie-in comic book series. The word "Adventures" has been used by several Superman themed TV and radio shows including: The Adventures of Superman, The Adventures of Superpup, The New Adventures of Superman, The Adventures of Superboy (animated and live action) and Lois and Clark: The New Adventures of Superman.
- This episode marks the first time in the Arrowverse where a season premiere takes place immediately following the previous season's finale. The second would be Season 5 episode "" which picks up exactly where "" left off.
- Clark references "Great Caesar's Ghost" to Perry White, a phrase the latter says in the TV series The Adventures of Superman.
- When J'onn told Winn to learn something his experts could not, Winn said "Challenge accepted." Quoting Barney Stinson's catchphrase from How I Met Your Mother.
- Cat's new assistant, Eve Teschmacher, is a reference to Lex Luthor's assistant from Superman: The Movie and its sequel, Superman II. The way in which Cat calls, "MISS TESSMACHER!" is a nod to Gene Hackman's version of Lex Luthor.
- Lena's quote, "Statistically speaking, of course, it's still the safest way to travel" is from Superman: The Movie.
- Winn mentions an earthquake that Superman stopped in the San Andreas fault, a reference to Superman: The Movie.
- When Superman narrowly saves man's family from drone's attack, the man from that family claims that he wants to get out of National City and return to Gotham. This is a reference to Batman's hometown in DC Comics.
- While complaining about not being told about the D.E.O. National City headquarters, Kara claims that a bat once bit her in the D.E.O. desert facility, which is impossible due to her invulnerability (unless this happened while she depleated her solar energy reserves and was powerless).
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