Green Gables household:
- Anne Shirley: An imaginative, talkative, red-headed orphan who comes to live with Matthew Cuthbert and Marilla Cuthbert. Anne is very sensitive and is pathologically insecure about the color of her hair. She exhibits categorical interest in everything romantic.
- Marilla Cuthbert: Matthew's sister, she is an austere but fair woman who objects to Anne's imaginative, unusual conduct on the grounds of them being part of the same group of behavioral misconducts that bring about dereliction of responsibility or produce a disrespectful personal image. Life experience with Anne, however, profoundly affects Marilla's ways; in a very early instance, she experiences first-hand how worthless a confession under duress could be. Although conservative and austere, she is fond of Anne and has the glimmerings of a sense of humor.
- Matthew Cuthbert: Marilla's brother, he is an overly shy albeit kind old man with a lumbering frame and above-average strength. Matthew takes a liking to Anne from the start and the two become fast friends. Because Marilla has primary responsibility for rearing the girl, he has no qualms about "spoiling" her and indulging her in pretty clothes and other frivolities.
- Diana Barry: Anne's bosom friend and a kindred spirit. Anne and Diana become best friends from the moment they meet. She is the only girl of Anne's age who lives close to Green Gables. Anne admires Diana for being pretty and for her amiable disposition. Diana lacks Anne's powerful imagination but is a loyal friend.
- Gilbert Blythe: A handsome, smart, witty and chivalrous classmate who has a crush on Anne the moment he sees her. Unaware of Anne's near-pathological sensitivity about her red hair, he tries to get Anne's attention by holding her braid and calling her "Carrots!" Anne's explosively hostile reaction only causes Gilbert to be more smitten. He makes several attempts to apologize, the failure of all of which do not seem to mar his admiration. He attempts apology one last time when he saves Anne from drowning; Anne crassly rebuffs this attempt, only to regret it almost immediately. Years later, he gives up his job offer of teaching at the Avonlea school so that Anne may live at Green Gables, upon which the two reconcile and become good friends.
- Ruby Gillis: Another of Anne's friends. Having several "grown up" sisters, Ruby loves to share her knowledge of beaus with her friends. Ruby is portrayed as traditionally beautiful with long golden hair. She is hysterical and suffers from consumption (tuberculosis).
- Jane Andrews: One of Anne's friends from school, she is plain and sensible. She does well enough academically to join Anne's class at Queen's.
- Josie Pye: A classmate generally disliked by the other girls (as are her siblings), Josie is vain, dishonest and jealous of Anne's popularity.
- Mrs. Rachel Lynde: A neighbour of Matthew and Marilla, Mrs. Lynde is an amalgamation of vices and virtues. She is industrious and helpful, and does work for the church, yet she is famous for being nosy and condescending Although she and Anne start off the wrong foot, owning to Mrs. Lynde's obnoxiousness and Anne's zero tolerance for such, they soon become very close. Mrs. Lynde is married and has raised ten children, although her husband, Thomas Lynde, is mentioned briefly and never speaks.
- Mr. Phillips: Anne's first teacher at Avonlea, Mr. Phillips is unpopular with students, because of his boring and crude ways. In case of Anne, he continually misspelled her name (without the "E") and punished only her among 12 pupils who arrived late. He is described as lacking discipline, and "courts" one of his pupils openly. (It was less frowned upon then as opposed to more contemporary times).
- Miss Muriel Stacy: Anne's energetic replacement teacher. Her warm and sympathetic nature appeals to her students, but Avonlea's conservative parents disapprove of her liberal teaching methods. She forms a special relationship with Anne, who views her as a mentor. Miss Stacy encourages Anne to develop her character and intellect, and helps prepare her for the entrance exam at Queen's Academy, where she finishes in a tie for first with Gilbert Blythe.
- Reverend and Mrs. Allan: The minister and his wife also befriend Anne, with Mrs. Allan becoming particularly close. She is described as pretty.
- Mr. & Mrs. Barry: Diana's parents. Mr. Barry farms. Near the end of the book, he offers to rent some tracts to help out Anne and Marilla, after Matthew's passing. Mrs. Barry has a severe personality, expecting her children to follow strict rules. After Anne accidentally gets Diana drunk, Mrs. Barry rejects the girl, forbidding Diana to have anything to do with Anne. This sanction is repealed after Anne saves Minnie May.
- Minnie May Barry: Diana's baby sister, whose life is saved by Anne when she comes down with croup.
- Miss Josephine Barry: Diana's aunt. Initially portrayed in a negative light, she is quickly charmed by Anne's imagination, and eventually invites her and Diana to tea. She refers to Anne as "the Anne-girl" and even sends Anne beaded slippers as a Christmas present.
- Mrs Spencer: Anne lives with her for a portion of her life. She is very mean and cruel as a result of her husband′s death. Anne is treated more as a maid in her home than as a daughter or friend.