Glameow first appeared in A Glamorous Encounter!, where she was shown performing an act to a group of wild Pokémon. Upon first seeing Glameow, Bianca became infatuated with the Glam Cat Pokémon and became determined to catch it, although Tepig was unable to keep up with Glameow and was knocked out by Shadow Ball.
Bianca later heard from a woman living nearby that Glameow's Trainer was a Co-ordinator who had abandoned her because she decided that Glameow wasn't good enough for Contests, and that ever since Glameow has been putting on shows for wild Pokémon in an attempt to prove herself to her former Trainer.
This made Bianca even more determined to catch Glameow and challenged her again using Vanillish and later Mienfoo. Both Pokémon were unable to keep up with Glameow and were defeated. With one last option, Bianca sent out Larvesta. Larvesta managed to stop Glameow by attacking with Bug Buzz and then wrapping her up with String Shot. However, Glameow managed to escape the web and attack with Slash, while Larvesta countered with Flame Wheel. The resulting explosion knocked Glameow out. After the battle, Bianca expressed her awe of Glameow's talent and asked Glameow to come with her. Glameow agreed and Bianca captured her in a Poké Ball.
In Facing the Live Wire!, Glameow was used to battle Poppy's Pachirisu, in an attempt to calm the hyperactive EleSquirrel Pokémon. However, Pachirisu was able to run rings around Glameow and paralyse it with Thunder Wave. Despite this, Glameow was able to strike Pachirisu with Slash, sending it flying into a tree and knocking it out.
In A Big Stunky!, Glameow was angered when a wild Stunky accidentally got her dirty with its Sludge Bomb. She battled it out of anger and was defeated when Stunky got her dirty once more. Bianca's desire to catch the Stunky put Glameow on the back foot, as she believed that Bianca was taking its side over hers, and she ran away. After Bianca found her again, she reassured Glameow that she didn't prefer Stunky over her and the two agreed to work together to catch the Stunky. During the rematch with Stunky, Glameow managed to overcome her aversion to uncleanliness and learned Play Rough, defeating Stunky and allowing Bianca to catch it.
Glameow is a very proud Pokémon who always attempts to make herself as glamorous as possible. This extends to battles, where she prefers flashy moves that look mimic Contest battles. This desire to be dazzling stems from her being abandoned by her former Trainer, a Co-ordinator who deemed Glameow too ugly for Contests. Due to this, she is rather distrusting of humans, although she eventually formed a bond with Bianca after witnessing her own talents.
In A Big Stunky!, Glameow was shown to hate getting dirty and uncleanliness in general, as she was shown to take offence to a wild Stunky getting her dirty. In the same episode, Glameow overcame this trait slightly by learning Play Rough, although her rivalry with Stunky remains unchanged.