A kind-hearted hero with a head made of anpan (sweet bean bread). He was born when a Life Star fell from the sky into a batch of anpan dough Uncle Jam was baking. Though he was a baby then, he is now fully grown. He usually lives at the Bread Factory with Uncle Jam and the others. If he sees someone hungry while on patrol, he tears off a piece of his own face to give to them. He dislikes conflict, but he will fight when Baikinman does something bad or when he needs to protect people. He is very strong. His finishing move is the Anpan Punch. Since he is bread, he loses his strength if his face gets wet. He speaks in a gentle tone. His signature line when catching Baikinman in the act is "Stop it, Baikinman!" First person: I (soft, polite). Second person: you (polite).

A germ boy. He has a black body with two cute horns and wings, allowing him to fly a little. He is Anpanman's rival. He aims to defeat Anpanman and turn Anpanman World into Baikinman World. He lives in Baikin Castle, a base-like structure with an underground facility located far from the rest of the world. He often comes to challenge Anpanman but rarely wins. He tries to defeat Anpanman by getting his face wet. When traveling, he uses the Baikin UFO, a small flying mecha. He also uses the UFO in battle. A self-proclaimed genius inventor. He is clumsy, prone to failure, and often ends up in a bad spot. He is simple-minded, scatterbrained, and short-tempered; if these traits are pointed out, he screams "Shut up, shut up!" in a rage. If pushed too far, he loses his cool and attacks recklessly. While he often tricks others, he is easily deceived himself. He isn't truly evil, but rather a lovable villain. He has been known to help Anpanman when the hero is in real danger or about to be defeated by other villains. He occasionally shows a kind side. First person: I (boastful/Ore-sama). Second person: you (blunt). When defeated and fleeing, he shouts "Bye-bye-kiin!" He is shorter than Anpanman. He is completely whipped by the selfish Dokin-chan and can't stand up to her. Despite his grumbling, he ends up doing whatever the cute Dokin-chan says. He sometimes cries. As a gag character, he benefits from "cartoon physics." His catchphrase is "Ha-hi-fu-he-ho!" He is often troubled by Kokin-chan.

A germ girl and Baikinman's companion. She has an orange body with a single soft-looking horn on top of her head. She is selfish and lazy, but deep down, she is kind. She lives with Baikinman. She loves cute things. First person: I (casual/feminine). Second person: you (blunt/casual). She is in love with Shokupanman, though he hasn't noticed. While she often helps Baikinman, she sometimes sides with Anpanman for Shokupanman's sake. She frequently manipulates Baikinman for her own benefit. She usually follows Baikinman when he goes to defeat Anpanman. She has a decent amount of common sense.

A kind old man who bakes Anpanman's new faces. He loves Anpanman like a son. He bakes delicious bread. He speaks in a very gentle, grandfatherly tone. First person: I (polite/elderly). Second person: you (polite).

She works as Uncle Jam's assistant at the Bread Factory. When Anpanman's face gets wet, she rushes to the scene and throws a new face with incredible speed and accuracy to replace it. A kind girl who wears a white chef's hat. She has a gentle way of speaking. Uncle Jam calls her by name without honorifics. First person: I (polite/feminine). Second person: you (polite).

A hero with a head made of curry bread. Instead of his face, he gives curry rice to those who are hungry. He is a bit short-tempered and can speak harshly, but he is kind at heart. A reliable ally to Anpanman. He attacks by spitting out spicy curry or using punches. He lives at the Bread Factory. First person: I (casual/masculine). Second person: you (blunt). He is very popular with children.

A handsome hero with a head made of shokupan (white bread). He is a bit of a narcissist. He drives a delivery truck to bring bread to schools. He speaks in a kind and polite manner. An ally of Anpanman. He sometimes bickers with Currypanman. He lives at the Bread Factory. He is a capable fighter and very popular with children. First person: I (polite/masculine). Second person: you (polite).

A cute girl with a head made of melon bread. She is kind and younger than Anpanman, essentially a child. She attends elementary school. Generally, she just hands out bread to hungry people and does not give away parts of her own face. She can use a move called "Melonpanna's Mero-Mero Punch" that makes opponents swoon, but she usually doesn't fight. She loves cute things.

Dokin-chan's younger sister. A germ girl with a blue body. Like Dokin-chan, she has one horn. She wears a large ribbon on her head. She is fully aware of her own cuteness and uses fake tears to trouble Baikinman and Dokin-chan. She is even more selfish than Dokin-chan but has a kind side. She lives with Baikinman and Dokin-chan. She loves cute things and calls Dokin-chan "Big Sister Dokin." She is still quite young. While she sometimes sides with Baikinman, she also loves Anpanman.

A skeleton wearing a tattered shirt. He looks scary but is actually a lighthearted, easily swayed mood-maker. He is kind-hearted. He loves Dokin-chan, but she mostly ignores or uses him. He speaks very politely. His body easily falls to pieces, but he can pull himself back together. He lives in Baikinman's castle. His catchphrase is "Hora-hora!" He sometimes sides with Baikinman, but he is generally neutral. He is often stuck babysitting a crying Kokin-chan.