The 55-year-old actor was one of many stars to attend the I Am The Highway: A Tribute to Chris Cornell eventat The Forum in Los Angeles, California, on Wednesday, and had an especially sweet role.
About halfway through the five-hour show, Pitt -- wearing an all-black outfit and a newsboy cap -- introduced 14-year-old Toni Cornell, one of the late singer's three children, who performed with Ziggy Marley.
"It's my privilege to introduce to you a very special duet," Pitt began. "Just her third time on the mic, Toni Cornell and Ziggy Marley. Give it up!"
The pair went on to wow the crowd with a performance of Bob Marley's "Redemption Song."
In addition to introducing Toni Cornell, Pitt also posed with her and her brother, 13-year-old Christopher Cornell.
Pitt and Cornell's friendship dates back to the '90s, when the musician's song, "Outshined," was featured in Pitt's movie, True Romance. Throughout the years, the pair grew closer, with Pitt gushing about Cornell in interviews and Cornell attending Pitt's movie premieres. The actor's daughter, Zahara, also reportedly attended Toni Cornell's 2010 birthday party.
The tribute concert on Wednesday, hosted by Jimmy Kimmel, raised over a million dollars for the Chris and Vicky Cornell Foundation and The Epidermolysis Bullosa Medical Research Foundation. In addition to Pitt, celebs including Josh Brolin, Leonardo DiCaprio, Christian Bale, Tom Hanks, Courteney Cox, Kaley Cuoco and David Spade attended the event.
While Toni Cornell's performance was certainly one of the more memorable ones of the night, Rita Wilson, Chris Stapleton, Adam Levine, Miley Cyrus, Ryan Adams and Taylor Momsen also took the stage. Both of Cornell's previous bands, Soundgarden and Audioslave, performed as well.