Keechant Sewell, 49, is a 23-year veteran of the Nassau Police Department in nearby Long Island, where she became chief of detectives in September 2020.
For Mr Adams, the move fulfils a campaign pledge to name a female commissioner.
The NYPD is the largest police force in the US.
Speaking to media on Wednesday morning, Mr Adams – a former NYPD captain – said that women often are “sitting on the bench” and “never allowed to get in the game” when it comes to policing.
“That is stopping today,” he said.
Ms Sewell, who is originally from the New York borough of Queens, previously served in New York’s Nassau County narcotics and major case units, and as a hostage negotiator.
When she takes over the department in January, Ms Sewell will also become only the third black commissioner to take the helm of NYPD.
Ms Sewell said she was “mindful of the historic nature of this announcement” and hopes to improve relations between the police and New York City’s residents.
“I bring a different perspective to make sure the department looks like the city it serves, and making the decision, just as Mayor Adams did, to elevate women and people of colour to leadership positions,” she said.
She added that as commissioner she plans to be “laser focused” on violent crimes particularly gun crimes.
Bill de Blasio, the outgoing mayor, often had a difficult relationship with the NYPD. In 2015, for example, officers turned their backs on Mr de Blasio at the funeral of a police officer killed in the line of duty.
The decision to name Ms Sewell as commissioner was praised by Patrick Lynch, the president of the largest police union in the city, the Police Benevolent Association of the City of New York.
“New York City police officers have passed our breaking point. We need to fix that break in order to get our police department and our city back on course,” he said in a statement. “We look forward to working with her to accomplish that goal.”
The NYPD employs nearly 35,000 police officers, of whom approximately 18% are women.