Hopkins is a character of the day who appeared in Holy Matrimony!, as James's butler. He was nameless in the Japanese version.

Hopkins first appears when Ash and his friends are looking at a missing poster that shows James as a kid. He comes and asks them if they have seen James. When Ash tells him that they have seen James, he takes them in a limousine to James's house. When Ash tells him that it is the biggest mansion he has ever seen, Hopkins yells at him and tells him that it is only his favorite Pokémon, Growlie's doghouse and shows James's true mansion. Hopkins is the first to tell Ash and his friends that James's parents are "dead" and that he has to marry his fiancée Jessebelle within twenty-four hours or the whole entire property will be donated to charity.

Later in the episode, when Jessie and Meowth force James to return home, Hopkins prepares James for his marriage with Jessebelle. He later throws Ash, Pikachu, Brock, Misty, Jessie, and Meowth out of the mansion's dungeon. Near the end of the episode, Hopkins is feeding Magikarp in the fountain outside of the mansion when he is knocked into the water by Jessebelle, who was trying to get away from Growlie.

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