The series consists of mostly stand-alone episodes which retell different fairy or folk tales. Despite the title, they are not all based on fairy tales collected by the Grimm Brothers.

Panty and Stocking Anarchy, the angel twin sisters, have even more ghosts to exorcize in Daten City, thanks to the failed opening of the Hell Gate. They must continue their ghost hunt alongside their longtime rivals, the sisters Scanty and Kneesocks Demon, who must earn Hell Coins to return to Hell. On top of that, the Demon sisters are staying at the church with Garterbelt, the priest in charge of the Anarchy sisters. These two polar opposite duos will have to set aside their differences if they wish to collect enough Heaven and Hell Coins to complete their mission and return to their respective realms.

Lua is a saintess candidate who possesses the power of healing. But her ability had one flaw: she could only heal others by transferring their wounds onto herself. Because of this, others bullied her, calling her the "Fallen Saintess." But it didn't bother Lua because her best friend Arianne always stood up for her. One day, Lua's crush, Commander Garrett, was on the brink of death from a beast attack. Lua healed him, which left her on the verge of death. When she woke up, she learned that all the credit was given to Arianne, and she finally saw her best friend's true color. Devastated, Lua is lost and helpless when the second prince appears in front of her with a tempting offer. What would happen to Lua as she begins her new life as a villainess?

Toto has been dreaming about adventuring with other people for as long as he can remember. Despite his hero title, he still remains without allies due to his timid personality. Therefore, when three women: Ciel, Anemone, and Goa suddenly request to join him, Toto is overjoyed. Unbeknownst to him, they are all assassins assigned to eliminate him! While Toto resolves to protect his would-be killers, the women fight over who can finish off the hero. As Toto remains oblivious of his new party members' true intentions and finds himself passing out every time he gets flustered, the four of them embark on their peculiar adventure into the greater world.