He will play Calvin Shaw, a former FBI agent incarcerated for killing one of his informants, reported Variety.
Perrineau's casting comes after Thomas Gibson was fired from the show following an on-set altercation with a producer.
Prior to Gibson's highly-publicized exit, longtime star Shemar Moore also left the show.
However, the show also brought on many new series regulars for the new season, including "Criminal Minds" alum actors Paget Brewster, Adam Rodriguez and Aisha Tyler, who was upped to a regular role.
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