There will be a thorough investigation of all use of force during three days of unrest following George Floyd's death in Minnesota and other recent deaths of people of color in encounters with police, Commissioner Danielle Outlaw said at news conference.
Police also fired nonlethal bullets into the crowd of protesters on the Vine Street Expressway on Monday, and more than two dozen people were arrested.
Outlaw said there have been 692 arrests as of Tuesday afternoon and more than 25 officers injured during the protests.
She did not provide a breakdown of charges but said the day before that more than half the people arrested had been cited for failure to disperse and breaking a curfew set by city officials to try to maintain order since Saturday.
The department has also created "looting teams," groups of officers focused on deterring damage to storefronts and the theft of merchandise, Outlaw said.
The curfew on Sunday and Monday was 6 p.m., and Mayor Jim Kenney said it would be 8:30 p.m. on Tuesday so voters can feel safe going to the polls for the Pennsylvania primary election and getting home afterward.
Kenney condemned "armed vigilantes" who appeared Monday night with baseball bats near a police precinct house in the Fishtown neighborhood, calling them unacceptable and saying he was "deeply troubled" by officers who took pictures with them and gave them high-fives.
"We do not condone vigilantes," Kenney said. "We tolerated it for too long last night, and that was a mistake."