Anne is a highly imaginative, talkative 11-year-old orphan with bright red hair. Having bounced between foster homes that only used her for labor, she desperately longs for love and a permanent family. She relies on her rich fantasy life to cope with the harsh realities of her past, maintaining a remarkably hopeful outlook on the future. Her striking honesty and unique perspective quickly begin to charm the reserved residents of Avonlea.

Marilla is a practical and rigid spinster in her mid-50s who lives with her brother at Green Gables. She initially intends to send Anne back to the orphanage, finding her talkative nature unnatural and exhausting. Beneath her strict exterior, she possesses a dormant sense of humor and slowly awakens to deep maternal affection for the young girl.

Matthew is an exceptionally shy, 60-year-old bachelor who dreads interacting with women or strangers. He lives at Green Gables with his sister and originally intends to adopt a boy to help with heavy farm labor due to his worsening heart condition. Instead, he is instantly transfixed by Anne's chatter and becomes her most steadfast defender.

Diana is a pretty, dark-haired girl who lives on the farm next to Green Gables. She possesses a merry expression and a thoroughly sweet demeanor. While she lacks Anne's intense creative genius, she eagerly joins in her imaginative games, becoming the true and loyal companion Anne always desired.

Gilbert is a handsome and popular student known for his intelligence and mischievous nature. Used to charming his classmates effortlessly, he makes a critical error by teasing Anne about her red hair. This single action ignites a fierce academic and personal rivalry between them that dominates their school years.

Mrs. Rachel is Avonlea's nosy but well-meaning community leader who prides herself on speaking her mind at all times. She is highly skeptical of orphans and holds strict societal views. Her blunt, uninvited criticism of Anne's appearance leads to an explosive first encounter.

Miss Stacy is an innovative and inspiring educator who brings a fresh, hands-on approach to learning in Avonlea. She encourages her students to think critically and express themselves. She recognizes Anne's potential early on and works directly to prepare her for higher education.

Mrs. Barry is Diana's mother, a strict and particular woman who carefully monitors her daughter's companions. She is quick to judge based on appearances and societal expectations, making her highly wary of Anne's unconventional background and prone to harsh conclusions when accidents occur.

Mrs. Allan is the pleasant, young wife of Avonlea's new minister. She brings a spark of fresh energy to the traditional town. Kind, supportive, and open-minded, she quickly earns Anne's adoration and becomes a trusted confidante who never laughs at the young girl's mistakes.

Aunt Josephine is Diana's formidable, wealthy great-aunt from Charlottetown. Known for her demanding and sour disposition, she expects perfect behavior from her family. However, she finds herself surprisingly amused by Anne's courage and forthright nature when the girl arrives to apologize.

Minnie May is Diana's toddler sister. When she falls severely ill during a time when all the town's adults are away, her dire situation provides a critical test of Anne's capability and past experience with raising children.

Mr. Phillips is the initial schoolmaster in Avonlea. He is often partial to older students and heavily doles out humiliating punishments. His lack of empathy makes Anne's early school days particularly challenging.

Mrs. Spencer is an acquaintance of the Cuthberts who travels to the Nova Scotia orphanage to retrieve a girl for herself. Due to a miscommunication, she mistakenly brings back a girl for Green Gables instead of the boy they requested, setting the events of the story in motion.

Mrs. Blewett is a small, shrewish-faced local woman widely known for being a terrible worker and driver of her servant girls. She immediately offers to take Anne off Marilla's hands to use her for hard household labor.

Josie Pye is a classmate of Anne's and her primary rival among the girls. She frequently doubts Anne's abilities and actively instigates risky dares, testing Anne's fierce pride and leading to physical injury.

Jane is one of the local Avonlea girls who becomes part of Anne and Diana's close-knit circle of friends. She actively participates in their imaginative games and eventually joins them in their advanced academic studies.

Ruby is a classmate who occasionally draws Anne's ire due to her friendly association with Gilbert Blythe. She is highly focused on boys and current fashions rather than academic achievements.