Main and Supporting

Calamity Jane

Action Girl: Naturally, though she often has to use skill, set-up, and diversions to win as much as she does physical prowess as she's often up against powerful foes.
Amazing Technicolor Population: She has skin as pale as snow.
Agony of the Feet: When Jane gets cornered by the triplet bandits in episode "As Easy as One, Two, Three...", they force her to be chased barefoot, obviously into trying to invoke this trope, but she's able to escape them and call her horse.
Daddy's Girl: Jane is this to her father despite him walking out on her and her mother at a young age, thanks to all the stories of heroism and valor her mother told about to Jane about him before she died. Liam's criminal boss tries to use this to his advantage to deter Jane from interfering in his bank robber scheme by having Liam pretend to be her father.
Losing a Shoe in the Struggle: She loses both her boots in “I'd Rather Be in Philadelphia“ during her struggle against the Neo-Confederate soldiers.
Significant Green-Eyed Redhead: He has red hair, green eyes, and is the series protagonist.

Joe Presto

Butt-Monkey: If something bad happens, it often happens to him first. Then there's his long-suffering exasperation with taking part in Jane's wild adventures.
Martial Pacifist: He will use a shotgun if he has to, but prefers to not use lethal or serious force. He loads it with rock salt.
Older Sidekick: He's old enough to be Jane's grandfather, acting as both her aid and mentor.

Wild Bill Hickhock

Ambiguously Evil: He often has an in-road with criminals and can be extremely menacing, but he usually seems on the up and up. Usually.
The Not-Love Interest: Despite a lot of fiction pairing him and Jane together, here they are just old friends.
Professional Gambler: Most often seen sitting with a cards in hand and winnings on the table.

Quanna Parker

Captain John O’Rourke

It's All My Fault: In "The Final Curtain", Captain John O'Rourke reveals he witnessed the Abraham Lincoln assassination as a child and felt responsible because his older brother, who should've been guarding the President, chose to sit by him instead.
My Country, Right or Wrong: Captain O'Rourke of the US Cavalry explains even his unconscionable orders of killing innocent Indians with "I have my orders." Chena of the Comanche says not to hold it against him, since if one does not stick to his principals (In O'Rourke's case, the principal of serving his country) then there is nothing left.

Other characters

Bill Doolin

Napoleon

John Wesley Hardin

Jeremiah Wilkinson

Elder Donovan

Mr. Filbert

Ellie

Amanda

President Grant