- Esther Greenwood, the protagonist of the story, is an ambitious English Major from Boston. Having won a summer job as a "guest editor" for Ladies' Day magazine, she lives at the Barbizon hotel[4] (referred to in the novel as the "Amazon" hotel) in New York City, along with the other young women who were selected as guest editors. Esther experiences increasing mental instability during her time in New York and over the following weeks. Her realization that she has no idea what she will do after graduation, combined with professional setbacks, social alienation, the trauma of narrowly avoiding being raped, and the feeling that she simply does not fit into the culturally acceptable role of womanhood, escalate Esther‘s emotional state of fear and panic. Though it is not immediately apparent, unresolved grief at the death of her father when she was 8 also affects her. Having returned to live with her mother in the Boston suburbs, and experiencing increasing insomnia, loss of appetite, and an inability to read or write, she becomes fixated on—and later attempts—suicide. Before her precipitous decline in mental health, Esther was known as a hardworking student, with an impressive record of excellent grades and a history of winning awards and recognition for her achievements. With the end of that era in sight, Esther is directionless, having only a vague idea she might go into publishing or become an author and poet. This existential quandary results in increasing self-absorption, leaving her prone to feeling detached and tired. She leaves her friend Doreen with a man they just met, after having been asked to stay to help protect her. Later, Doreen returns to the hotel, very drunk and asking for her. While Esther is helping Doreen to her room, Doreen vomits and passes out. Esther leaves her to sleep it off on the corridor floor, rather than deal with the resultant mess.
- Doreen, another guest editor at Ladies' Day magazine, is a daring and rebellious young woman, and Esther's best friend in New York. Esther finds Doreen's confident personality and free spirit appealing but troublesome, as she longs to be free of society’s constraints, but fears the possible consequences. Esther admires Doreen’s appearance, humor, personality, and even smell, which she describes as musky and sweet, like freshly crushed ferns. Ultimately, Esther’s fear leads her to reject Doreen and resolve to have little more to do with her, choosing instead to befriend Betsy, a prototypical “good girl”. However, after failing to be accepted into her desired writing program, Esther impulsively writes to Doreen to ask if she can stay with her, but seeing the deterioration of her handwriting frightens her and she never sends the letter.
- Joan, an old acquaintance of Esther, coincidentally ends up in the same mental hospital. Joan also had dated Buddy Willard, but tells Esther later that she was more interested in maintaining a relationship with Buddy's parents, whom she idealizes as more concerned and caring than—and therefore, superior to—her own. At the hospital, she and Esther engage in a quiet competition to recover first, an apparently common situation among the patients. Upon abruptly entering Joan’s room, Esther finds her in bed with DeeDee, another female patient. Esther then reflects on other women she has known who have sex with women, wondering what motivates them. When Joan later makes an ambiguous overture to her, Esther cannot figure out whether it was a pass or a gesture of friendship. In response, Esther tells Joan she never has liked her. Later, when Esther hemorrhages as a result of her first sexual experience, Joan helps her get to the emergency room. Joan eventually dies by suicide at the mental hospital. Esther attends her funeral.
- Doctor Nolan is Esther's doctor at the mental hospital. A beautiful and caring woman, her personal sensitivity and professional ability combine to make her the first woman in Esther's life with whom she feels she can fully connect. Nolan prescribes shock therapy and ensures that it is done correctly, which leads to positive results.
- Doctor Gordon is the first psychiatrist to treat Esther. Self-obsessed and patronizing, he subjects her to poorly administered electric shock treatments that traumatize Esther and utterly fail to help.
- Mrs. Greenwood, Esther's mother, loves her daughter, but is constantly urging Esther to mold herself into the societal ideal of white, middle-class womanhood—a goal for which Esther feels no desire at all.
- Buddy Willard is Esther's former boyfriend from her hometown. Studying to become a doctor, Buddy wants a wife who mirrors his mother, and hopes Esther will be that for him. Esther adores him throughout high school, but—upon learning that he is no longer a virgin—she loses respect for him and labels him a hypocrite. However, she feels compelled to postpone ending their relationship when Buddy is diagnosed with tuberculosis. He eventually proposes marriage, but Esther rejects his proposal, telling him that she has decided to never marry. Buddy is shocked and responds that Esther is crazy.
- Mrs. Willard, Buddy‘s mother, is a dedicated homemaker with strict, conservative views about both the proper social roles for women and what constitutes sexual propriety. She is set on Buddy and Esther marrying. Joan loves Mrs. Willard and feels that she is the mother Joan always wanted and never had.
- Mr. Willard, Buddy Willard's father and Mrs. Willard's husband, is a good friend of Esther’s family.
- Constantin, a simultaneous interpreter at the United Nations, is an acquaintance of Mrs. Willard, who sets him up with a blind date with Esther while she is in New York. His alluring foreign accent and sophistication are very attractive to Esther, who contemplates giving her virginity to him when they return to his apartment. Puzzlingly, he chooses instead to spend the night sleeping chastely beside her.
- Irwin is a tall but rather ugly young man, who is the first man Esther has sex with, an initiation that causes her to hemorrhage. He is a "very well-paid professor of mathematics" on the make, and invites Esther to have coffee when they meet, unaware that she is on leave from a mental hospital. Unfortunately, penetrative sex with Irwin causes Esther to hemorrhage, a rare but not unheard of occurrence. As a result, he hastily pays for a cab and sends Esther “home”.
- Jay Cee is Esther's boss at Lady’s Day. She is very intelligent and capable, so "her plug-ugly looks didn't seem to matter".[5] She is responsible for editing Esther's work, which she does with a strictness that devastates Esther’s self-esteem.
- Lenny Shepherd, a wealthy young man and disc jockey living in New York, invites Doreen and Esther for drinks while they are on their way to a party. They go together to his place. Doreen asks Esther to stay with her in case Lenny “tries anything”, but Esther leaves. Doreen and Lenny start dating, taking Doreen away from Esther more often.
- Philomena Guinea, a wealthy, elderly lady, is the person who endowed Esther's college scholarship. Esther's college requires each girl who is on scholarship to write a letter to her benefactor, thanking him or her. Philomena invites Esther to have a meal with her and is taken with the student. Philomena had been committed at an earlier point in her life, and she insists on covering the cost of an expensive, private mental hospital for Esther, thus saving her from committal to a state-run institution. The inspiration for Philomena is believed to be Olive Higgins Prouty, an author who financially supported Plath before and after her stay in psychiatric care. Prouty struggled with mental breakdowns before meeting Plath, which may have been a direct reason for why she chose to pay for her scholarship.
- Marco, a Peruvian man and friend of Lenny Shepherd, is set up to take Esther to a party, and behaves misogynistically. Reflecting on him, Esther muses that "Women-haters were like gods: invulnerable and chock-full of power".[6] He assaults her, and attempts to rape her.
- Betsy, another guest editor at the magazine, is a "good" girl from Kansas whom Esther strives to be more like. She serves as a foil to Doreen. Esther finds herself torn between daring to be like Doreen and wanting to emulate Betsy.
- Hilda, also a guest editor, arouses Esther’s dislike with her callous attitude and cruel comments about the Rosenbergs as they await imminent execution.
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