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Madame Catherine first appeared in Summer of Discovery!. She ordered Team Rocket, who had gone undercover as cooks, to prepare a meal for the first day of the Summer Camp. Afterwards, she was present at the official opening of the Summer Camp and told all participants Diantha had attended the camp too when she was young. Later she decided to give Team Rocket a raise after she was content with their work. During the rest of the Summer Camp arc, she continued to order Team Rocket around, but also gave them more raises.
In Battling Into the Hall of Fame!, she went looking for Team Rocket after they had taken a break from their work. She found them in the nearby forest where they claimed to be looking for ingredients for the next meal. However, right at that moment, Ash and his friends arrived on the scene after suspecting the cooks of having stolen Tierno, Trevor, and Shauna's Pokémon. After Pikachu uncovered the cage with the Pokémon in it, Team Rocket revealed their real identity, which greatly shocked Madame Catherine. After Ash and his friends managed to blast them off, she frustrated herself over the fact that Team Rocket could have earned their money fairly with cooking.