On their way to the next Johto League Gym in Olivine City, Ash and his friends pass through a town, where they see a herd of screaming girls running down the street. Brock chases after them, and Ash and Misty follow him. A mysterious man stops their pursuit and hands Ash a ball of yellow cloth. He assures them that he’ll be back later before running off, dropping his black hat in the process. Ash unwraps the blanket and finds a Smoochum inside.
Smoochum kisses Ash on the cheek. It leaps from his arms and smooches Misty as well, then it turns its attention to kissing Pikachu. Ash reads Smoochum's Pokédex entry and Brock adds that it uses kisses as its sense of touch. Smoochum soon retrieves the dropped hat and places it on its head. As it loses its bearings, Smoochum bumps into Brock, who puts the hat on his head. Then, the screaming girls rush over to Brock, squashing and elbowing the group in the process. Togepi, Smoochum, and Pikachu are thrown out of the chaos, and Togepi and Smoochum follow a Skiploom into an alley. Unable to get Ash's attention, Pikachu goes after them. Brock is pleased with all the attention and takes off the hat, but the ladies realize that Brock isn't who they were looking for and disband. The trio notices an advertising screen above them and realize the man they met earlier is a movie star named Brad. Misty then realizes Togepi, Pikachu, and Smoochum are missing.
Team Rocket reviews their robo-Skiploom's footage, and are pleased to see they have caught the attention of Togepi and Pikachu. Soon enough Togepi, Smoochum and Pikachu follow the mecha directly to into Team Rocket's hideout. James takes Togepi and Smoochum into his arms, while Jessie gets Pikachu out of a tight hole with some protective rubber gloves. Jessie puts Pikachu in a rubber sack, and begins cuddling Smoochum when Ash and his friends arrive. Ash sends out Bayleef and Totodile. Bayleef uses Razor Leaf to cut Pikachu out of the rubber sack while Totodile uses Water Gun to release James' grip on Togepi and Smoochum. Meowth tries to attack with the Robo-Skiploom, but Totodile blasts it away with Water Gun. With Team Rocket wet, Pikachu uses Thunderbolt, sending Team Rocket blasting off.
Meanwhile, Brad returns to where he met Ash's group, but is frustrated not to see them waiting for him as planned. He calls out for them, but this only attracts a crowd of loyal fans. Before they can get to him, his manager Vitzo pulls up and lets Brad get in the car, but he warns Brad about roaming the streets. Smoochum gets excited after seeming a limo, and Ash and his friends acknowledge that it must be Brad's, so they follow it to a large dome arena. As they queue up, the group quickly realizes that the situation is hopeless and decide to find another way to reach Brad.
Inside, Brad tells his manager that he cannot go on with the show until he gets his Smoochum back. Vitzo is unimpressed and suggests that Brad get rid of Smoochum in exchange for a tougher Pokémon to fit his image. Brad refuses and reveals that he was only a star because Smoochum believed in him and made him believe he could do it. Vitzo defends his comments and points out that Brad could find himself washing dishes again if he doesn't change his mind. Suddenly Brad thinks he hears Smoochum nearby, and he is correct as Ash attempts to climb a tree to reach a second storey window. Vitzo looks out the window and notices Smoochum. He closes over the curtains and tells Brad that the sound was some squealing fans. Vitzo then leads the movie star out of the room, reassuring him that he'll figure everything out. Ash and Smoochum call out, but Brad has already left the room. Inside, Ash and his friends attempt to talk to Vitzo and have Smoochum returned to Brad’s side. However, Vitzo claims that Brad no longer wants Smoochum. The admission comes as a shock to group, and Ash presses for more clarification. Brad emerges from his room and is thrilled to see Smoochum again. Smoochum leaps into its Trainer’s arms, but Vitzo is more concerned about Brad's public image and ushers everyone backstage.
Team Rocket uses their binoculars and watches Smoochum reunite with Brad. Jessie is charmed by Smoochum's adorable nature, though Meowth finds Jessie's behavior to be even scarier than when she is angry. Soon Brad leaves to get ready for his performance, and he leaves Smoochum in the group's care. Meanwhile Team Rocket steal two backstage guard's uniforms, and they toss the actual guards in lockers. Vitzo approaches the pair and orders them to throw Smoochum and Ash's group out of the building. Team Rocket escorts the group to a stage and then catches them with a net, but Smoochum falls out of the net. The Rocket trio reveals their true identities and performs their motto. James and Meowth grab a hold of the two controlling counter-levers and begin to pull their netted catches up and down for the fun of it.
Brad returns to the green room, and he then accuses Vitzo of throwing out the group and Smoochum. He rushes off to search for his beloved Pokemon. Meanwhile Jessie tries to convince Smoochum to get into a cage, but Smoochum doesn't want to. Meowth, playing with the drop cords on the stage, accidentally draws the curtains open, revealing themselves to all the audience. Jessie decides this is the perfect opportunity to fufill her actress ambitions, but the audience demands to see Brad—who is still backstage being held up by his manager. Hearing his Smoochum's cry, Brad runs onstage to save it, but Team Rocket is ready to battle. Jessie calls on Wobbuffet, but he is too taken by the crowd’s attention so he is quickly recalled. Using Weezing, James orders it to Tackle Brad, who easily evades it. Jessie sends out Arbok who uses Poison Sting, but Brad performs several backflips to evade it too. After evading another of Weezing's Tackles, Weezing slams into Jessie who releases Smoochum on accident. Brad catches Smoochum, and the crowd goes wild, but then is confused by Brad's affection to Smoochum.
Arbok's Headbutt misses and it makes Meowth drop the cords, resulting in Ash and his friends being freed from the net. Ash sends out Bayleef and she tosses Arbok to the ground with Vine Whip. James remains determined and has Weezing use Smokescreen to block everyone's view. Ash sends out Noctowl to clear the air, and once done, Brad commands Smoochum to use Sweet Kiss, sending Team Rocket into a daze. Pikachu uses Thunderbolt, sending Team Rocket blasting off once again. The crowd applause, but then Brad reveals that it wasn't an act, exciting them all. Brad declares that he and Smoochum have been partners for a long, and as Vitzo cringes at the glaring silence, the fans cheer for them both. Vitzo is thrilled by Brad's new sensitive angle and declares himself a "genius", though Ash's group glare at him in sarcasm. Brad walks up the fleet of stairs to thank the group for the assistance. He offers to give Ash something, and Ash hopes for a new starring role, but the "gift" turns out to be one of Smoochum's kisses. Ash falls down the stairs trying to avoid the overbearing affection, and Misty and Brock joke that a stuntman role would suit Ash perfectly.
Later, Ash, Misty, and Brock turn their attentions to an advertising screen on the streets, where they watch Brad and Smoochum co-star in a new movie. Brock then notices a lot of the fans have Smoochum dolls in their arms, and Ash remarks that Brad may be Smoochum's co-star from now on.