Every superhero needs their arch-nemesis, and Pretty Sammy's comes in the form of Pixy Misa. The normally shy and withdrawn Misao, Sasami's best friend and classmate, is chosen by Tsunami's rival Ramia as her representative of chaos and catastrophe. When hypnotised by Rumiya, Misao becomes Pixy Misa, a force of uncontrollable mischief bent on destroying Pretty Sammy. She is capable of conjuring up Love-love Monsters, bizarre creatures that are made by infusing ordinary objects with evil magic, to do her dirty work. Because she is hypnotised before transforming, Misao has no idea that she is really Pixy Misa.

Ramia is the second candidate for the crown of Juraihelm, and is confident that she will be selected until the royal council chooses Tsunami over herself. Enraged by the decision, Ramia makes it her sole purpose to scupper Tsunami's bid for leadership by creating a magical girl of her own, Pixy Misa. Despite masterminding her attempt to discredit Tsunami, she gets her little brother Rumiya to doing most of the dirty work, sending him off to summon Misa while she usually sits at home and watches.

Rumiya is Ramia's downtrodden and long-suffering little brother. Acting under the orders of his bullying sister, he makes frequent trips down to Earth to hypnotise Misao and transform her into Pixy Misa. While on his missions to Earth, he takes the form of a bird (purple in the OVA series, green in the TV series). Following his sister's orders and forcing Misao to change against her will is made doubly difficult for him after he develops a crush on her!