The retirement of the 23-year-old ex-University of Alabama star comes after an April 22 arrest on charges of disorderly conduct and resisting in his home town of Decatur, Ala.
Ravens General Manager Ozzie Newsome, who signed McClain to a one-year deal following his April 5 release from the Oakland Raiders, said the linebacker is leaving the game.
"Rolando let me know that he plans to retire from the NFL," Newsome said. "We have placed him on the reserve/retired list."
Selected eighth overall in the 2010 NFL draft, McClain was suspended for two games last season after clashing with head Coach Dennis Allen.
The Decatur arrest was the third in a 16-month span for McClain.
Prosecutors alleged he inciting a crowd during the incident, yelling "(expletive) the police!" as he was being taken into custody, the Baltimore Sun reported.
McClain had 246 tackles, 6 1/2 sacks and one interception in 41 career games with the Raiders.