The very same Joan of Arc, known as the "Maid of Orleans" (La Pucelle d'Orléans), who led the French army during the Hundred Years' War. In this story, she is called by the nickname "Tart." She is revered as a "Saint" and the "Maid" by soldiers and commoners alike. She is 17 years old, possesses unique magic to manipulate light, and has a poor tolerance for alcohol, getting drunk easily.

A magical girl from medieval France serving in the army to take care of Tart's daily needs. She is the daughter of the mercenary captain La Hire (Etienne de Vignolles), a famous comrade-in-arms of Joan of Arc. Usually a kind and gentle girl, it is said that once she loses her temper, her rage is unstoppable. She fights alongside Tart and the others. As the daughter of La Hire, she has traveled through battlefields with her father as an attendant, looking after Tart's group. She is a reliable person who deeply cares for her family and friends, and is even seen scolding her father for his heavy drinking. On the other hand, she is somewhat soft on Tart, whom she admires like an older sister; there are scenes where she appears to glare at the Dauphin Charles (Charles VII) when he kisses the back of Tart's hand. While fundamentally kind-hearted, being the daughter of the fierce general La Hire (the "Wrathful"), her anger switch can be flipped if her friends are attacked. When she "snaps," she displays terrifying rage, ferocity, and power. In this state, the blood drains from her face and only her ears turn bright red (a trait apparently inherited from her father), reaching a point where neither Etienne nor Melissa herself can control it. When Elisa made a veiled snide remark to Tart after Tart lost a sparring match (note that Tart herself didn't realize she was being insulted), Melissa wordlessly muttered, "Please spar with me as well," approached Elisa, and without further ado, sent her flying into the distance with a shoulder throw—a display of magic (physical). She also has a weakness for delicious things; upon learning from her father that a certain wine was tasty, she gulped it down, revealing a surprisingly high tolerance for alcohol. She is 15 years old.

A cool-headed magical girl from medieval Italy who stood up with Tart to save France. Supporting Tart with magic that manipulates "shadows," she fights on the front lines of the French army. Though she is reluctant to speak of it, she is said to be a descendant of a famous military commander. She is 18 years old. An Italian mercenary fighting alongside Tart. While known to those around her as Riz, her full name is Riz Hawkwood. She usually wears clothes resembling a sister's habit. In flashbacks, she wore a masculine outfit with a cloak. She has known Tart the longest. Generally expressionless and cool, she can be mischievous and enjoys teasing others, but has a soft spot for cute things like Tart's sister, Catherine. Those who know her say she always looks happy when eating sweets. (Furthermore, she always carries honey. High-sugar honey is excellent as a preserved food and energy source, which is not unusual, but in her case, it borders on obsession.) Like any girl, she is sensitive about being seen as older than her actual age; when a tactless Kyubey remarked, "Being older means being respected, so isn't it a good thing?", she glared at him and threw him away. Given that she went into a cold fury and slaughtered the deserters who killed Catherine, she might be the one person in this story you must never anger.

A medieval magical girl belonging to the prestigious Dragon Knights. She joined Tart's group to assist in the coronation of the King of France. The daughter of a consort of the Holy Roman Empire, she is prideful but responds with deep friendship to those she acknowledges. she loathes Cube (Kyubey) with a passion. As a member of the Dragon Knights, she was ordered to "measure the power of the 'Maid' who suddenly appeared and assist in the Dauphin Charles's coronation," leading her to travel with Tart. First person: I (watashi, polite/noble). She gives a noble impression. Her laugh is "Nyowahohoho." Due to her court upbringing, she uses lady-like speech and can be haughty, but she is fundamentally serious and has a gallant personality.

The mother of the masked magical girl sisters (Lapine, Corbeau, and Minou) belonging to the English Allied Forces, and the biological mother of the Dauphin Charles (later King Charles VII of France). She is the one who sought to destroy France and serves as the mastermind of this story.

A magical girl belonging to the English Allied Forces, the arch-enemies of Tart and the French army. One of Isabeau's daughters and the second of the three sisters. Before transforming, she wears clothes like a young lady of a good family, and her face behind the mask is quite handsome. Except when talking to her family, she speaks in an intimidating tone with unnaturally elongated sentence endings. On the other hand, she has a side that cares for her sisters, happily indulging Lapine's selfishness and unable to hide her joy that Minou grew up to be a "kind" girl. True to her name, which means "crow" in French, she wears a black crow mask with a long beak and a hooded cape shaped like bird wings.

A magical girl belonging to the English Allied Forces, the arch-enemies of Tart and the French army. One of the daughters of Isabeau of Bavaria and the youngest of the three sisters. She possesses a cruel personality, willing to discard allied soldiers, fellow magical girls, and even her own sisters as pawns for the sake of victory. She fanatically loves her "Lord" and biological mother, Isabeau, and swears absolute loyalty to her. Her wish upon contracting was "that no magical girl may ever be able to harm my mother."