Hopkins first appeared when Ash and his friends were looking at a missing poster that showed James as a kid. He approached them and asked them if they saw James. When Ash told him that they did, he took them inside a limousine and drove them to James's house. When Ash told him that it was the biggest mansion he had ever seen, Hopkins yelled at him and told him that it was only the doghouse for James's favorite Pokémon, Growlie, and showed them James's true mansion, which was even more massive. Hopkins was the first to tell Ash and his friends that James's parents were "dead" and that he had to marry his fiancée Jessebelle within twenty-four hours, or the entire property would be donated to charity.
Later in the episode, when Jessie and Meowth forced James to return home, Hopkins prepared him for his marriage with Jessebelle. He later threw Ash, Pikachu, Brock, Misty, Jessie, and Meowth out of the mansion's dungeon. Near the end of the episode, Hopkins was feeding Magikarp in the fountain outside of the mansion when he was knocked into the water by Jessebelle, who was trying to get away from Growlie.