"Leave it to Piyoko!" is a comedic anime series that revolves around the misadventures of Piyoko, a young alien girl from the planet Chichin, who is sent to Earth on a mission to kidnap the idol singer Love Love. Piyoko is accompanied by her loyal but bumbling subordinates, the De Chiko sisters—Gorgeous, Beauty, and Cutey—who assist her in her schemes. Despite their efforts, Piyoko and her team consistently fail in their attempts to capture Love Love, often due to their own incompetence and the intervention of Love Love's protective manager, Rabi~en~Rose.

The series is structured around episodic comedic scenarios, with Piyoko and the De Chiko sisters devising increasingly elaborate plans to kidnap Love Love, only to have them backfire in humorous ways. Piyoko's character is portrayed as naive and overly optimistic, contrasting with the more cynical and pragmatic De Chiko sisters. Love Love, on the other hand, remains largely oblivious to Piyoko's schemes, focusing on her career as an idol and maintaining her cheerful demeanor.

Throughout the series, the dynamic between Piyoko and Love Love evolves into a peculiar friendship, with Piyoko's repeated failures leading to moments of mutual understanding and camaraderie. The narrative also explores the relationships between the De Chiko sisters, highlighting their loyalty to Piyoko despite their frequent frustrations with her impractical plans. The series balances slapstick humor with lighthearted character interactions, creating a whimsical and entertaining atmosphere.

"Leave it to Piyoko!" is characterized by its playful tone and exaggerated comedic situations, with a focus on the absurdity of Piyoko's mission and the endearing quirks of its characters. The series does not delve deeply into dramatic or serious themes, instead prioritizing humor and the development of its central characters through their interactions and escapades. The episodic nature of the story allows for a variety of comedic scenarios, ensuring that the narrative remains engaging and dynamic throughout its run.