Authorities say Demetrius Antonio Montgomery has been charged with two counts of first-degree murder. Earlier, the police chief said a suspect was being questioned.
The two officers were shot during a domestic disturbance call at an apartment complex.
A police spokesman says the investigation is continuing.
Sean Clark, 34, and Jeffrey Shelton, 35, were the first officers from the Charlotte-Mecklenburg department fatally shot in the line of duty in more than a decade.
"It's a real tragedy for us, the officers, for the families, for the communities, that we've lost two in one incident," said Charlotte-Mecklenburg Police Department Chief Darrel Stephens.
Stephens said the two officers were responding to a disturbance call around 10:30 p.m. Saturday night at the apartment complex. They were shot around 11:15 p.m. in the parking lot during a struggle. Neither fired their weapon, Stephens said.
Clark and Shelton were taken to Carolinas Medical Center, where they later died. Clark had been with the police department for a year, and Shelton had worked there since 2001.
Both officers were married. Clark, a 1991 graduate of West Mecklenburg High School who had worked for the department for a little more than a year, and his wife were expecting a child. Shelton was a six-year veteran of the force.
"It's heartbreaking," Officer Bob Fey, a police spokesman, told WCNC-TV in Charlotte. "Just hearing a call like that going out over the air ... just hearing the dispatcher say those words over the air, `We have two officers shot in the North Tryon Division,' it just makes your heart skip a beat."
A Charlotte officer was last shot and killed on duty in 1993, when officers John Burnette and Andy Nobles died while chasing Alden Harden through a wooded section of southwest Charlotte, The Charlotte Observer reported on its Web site. Harden was convicted a year later and is one of 166 inmates on North Carolina's death row.
Last year, Officer Kayvan Hazrati survived when he was shot in the head while trying to serve a rape warrant in north Charlotte. He has yet to return to work.