Annie's boyfriend, Slim accompanies Annie on many of her adventures.
He is riding with Annie when her horse gets a loose shoe. He warns her not to go to Pete Grimm for help because of his misogyny. When Annie seems to join with the outlaws who steal Pete's money, he refuses to believe that she would really do it, and tries to chase her down to get an explanation. However, the trail is lost. He is delighted when she returns with the outlaws subdued and returns Pete's money.
Annie and Slim pass a man named Josiah Cleek selling real estate in a town called Starling Wells. Slim declares that is where he will build the house for Annie when they get married. She tells him Josiah is a swindler and confronts Josiah, but is not believed. He does not follow her when she leaves to inspect the land herself, believing she is on a "mad on" against men before buying a share of the land from Josiah. When Annie confronts Josiah again, he accompanies her to the land, asking if she's sure he can't live up to the promised land. When they get there, the false fronts fool everyone at first, and the townsfolk make fun of Annie. Slim tells Annie he will defend her if she gives the word because it's his place as a man to defend a woman. Annie reveals the ruse and takes down the swindlers without Slim's help and gets his money back.
Slim and Annie are riding into town when they get in a discussion about whether or not women are overall more honest than men. She challenges him to name a single female outlaw. When they reach the town, Annie is arrested by the Sheriff and eyewitnesses say that she is the one who robbed the local Wells Fargo bank and shot the cashier. Slim, enraged at the accusations, punches out the witness and is then arrested himself. In jail he makes a joke about their conversation, stating that Annie is a female outlaw. Annie breaks herself out of jail that night to prove her innocence, leaving Slim behind. He bemoans that he doesn't understand women. He is released from jail when Annie proves her innocence.
Slim, assisted by his friend Cal, plays a prank on Annie by writing a fake love letter from her to her nemesis, Grizzly Williams. When Annie finds out, she chases Cal and Slim to the pig sty.
After she complains about the Mayor, Slim encourages Annie to run for office and pushes her up on the podium. After she is elected, she learns that Slim has put her name on the dog-catcher ticket and traps him in the catcher cart.
At the fair, Slim is tricked into buying a watch that doesn't work. After Annie performs flawlessly at a shooting game, he tries his hand and fails. After making a wager to win some money for Slim, Annie is given a trick gun, and misses several shots. Annie hits him with the gun and discovers the ruse. After Slim makes fun of Annie for not noticing, she scares him onto the kiddie rides.
A friend of Slim's.
Cal helps Slim play a prank on Annie by writing a fake love letter from her to her nemesis, Grizzly Williams. When Annie finds out, she chases Cal and Slim to the pig sty.
Cal accompanies Annie and Slim to the fair, where he expresses his love for soda pop.
A misogynist blacksmith who refuses to service women. When Annie recovers his stolen money, he changes his ways.
Annie approaches him to fix a loose shoe on her horse, but he refuses as he believes all women are nothing but trouble for men. He is robbed by three outlaws who steal gold he had been saving up to bring to the bank. Annie seems to join up with them. Grimm tries to chase the outlaws with Slim's help, but loses the trail. When Annie returns with his stolen money, he changes his mind about women and offers free horse shoeing for women.
A man selling shares in a town called Starling Wells, he is a wanted swindler in the town of Leaping Falls.
Josiah is selling his shares when Annie recognizes him from his wanted poster. When confronted, he claims to be a prominent citizen, siccing the townsfolk onto her. She returns and confronts him again, but Josiah, who had prepared, insists that everyone see Starling Wells for themselves. He has erected fake cardboard fronts, but Annie quickly sees through the ruse and exposes him. He pulls a gun on her, but she overpowers him and his accomplice.
An outlaw that poses as a woman.
Grimes, a wanted man in the area for over a year, decides to pose as a woman to avoid the heat. Pretty Face, robs the local Wells Fargo Bank, shooting a cashier twice. The next night, he robs the Long Chance saloon. Annie, who has been accused of robbing the Wells Fargo, follows him and, seeing through his ruse because he lights his own cigarette, overpowers him and turns him in to clear her name.
Two outlaws, Syd and Bill, who are brothers and famous bank robbers.
Having just come from a successful hold up, the brothers are searching for a hideout. They find the local schoolhouse with Annie, who is filling in as teacher, preparing her lessons inside. Taking her by surprise, they tie her up, but she frees herself and turns the tables, overpowering them.
Annie's "arch nemesis", he becomes besotted when he receives a love letter he thinks is from her.
Grizzly approaches Annie and declares his love, but she rebuffs him. He reads a love letter signed by Annie to Cal and Slim, not knowing they are the real authors. They encourage him to try with Annie again, and Grizzly approaches Annie with a second letter that evening. After reading it to her, she scares him off. Later she goes to his cabin and has fun at Grizzly's expense, covering him with dust and dropping boards on his head before making sure he knows she is not interested and scares him off once and for all.
The town's mayor.
Square John runs for Mayor and wins re-election. When Annie learns she has been entered in the wrong race against him, she puts him in the dog-catcher's cart.