Bettie Jones, 55, was one of two people fatally wounded early on Saturday after officers responded to a domestic violence call on the city's West Side.
Chicago police said in a statement that officers "were confronted by a combative subject resulting in the discharging of the officer's weapon".
"The 55-year-old female victim was accidentally struck and tragically killed," the statement added.
The department, which is already facing intense scrutiny over the use of deadly force, said it extended its "deepest condolences to the victim's family and friends".
Quintonio LeGrier, 19, who lived upstairs from Ms Jones, was also fatally wounded and later died in hospital. Authorities said the college student who was home on holiday break prompted the domestic violence call.
His mother, Janet Cooksey, told the Chicago Tribune her son was not armed with a gun.
"He had a bat," she said.
Mr LeGrier's father, told the Chicago Sun-Times his son had attempted to bust through his bedroom door, prompting him to call police.
Antonio LeGrier said he also called Ms Jones to warn her that his son was a "little irate" and to not open her door unless police arrived.
When officers did arrive, the teen's father said he heard Ms Jones yell, "Whoa, whoa, whoa!" just before gunshots rang out.
He said he made his way downstairs where he found his son and Ms Jones lying in the foyer.
The shooting comes amid of a federal civil rights investigation into the Chicago Police Department's use of deadly force.
The probe was launched earlier this month after the release of a video showing a white officer shooting black 17-year-old Laquan McDonald 16 times in 2014.
The officer, Jason Van Dyke, is charged with first-degree murder.
Both Ms Jones and Mr LeGrier were black. Police have not revealed the race of the police officer involved in Saturday's fatal shooting.
The case is being investigated by the city's main police oversight agency, said Chicago Mayor Rahm Emanuel, who has faced calls to stand down amid the accusations of police misconduct.
Reverend Marshall Hatch said in a statement early on Sunday that the latest shooting showed how "deeply dysfunctional the relationship is between this department and its citizens".
He added: "We need relief in Chicago."
Relatives of Mr LeGrier, including his mother, wore sweatshirts adorned with "Rahm Failed Us" during a prayer vigil held in honour of both victims on Sunday.
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