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, Courtney 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.
Cornell was found dead in his Detroit hotel room on May 18, 2017. He was 52.
Chris Cornell with daughter Toni Cornell
Chris Cornell with daughter Toni Cornell
NEW YORK, NY - APRIL 18: Chris Cornell with family attend 'The Promise' New York Screening at Paris Theatre on April 18, 2017 in New York City. (Photo by Paul Zimmerman/WireImage)
LOS ANGELES, CA - MARCH 25: Musician Chris Cornell (R) and Toni Cornell celebrates Elton John's 70th Birthday and 50-Year Songwriting Partnership with Bernie Taupin benefiting the Elton John AIDS Foundation and the UCLA Hammer Museum at RED Studios Hollywood on March 25, 2017 in Los Angeles, California. (Photo by Michael Kovac/Getty Images)
TORONTO, ON - SEPTEMBER 11: Musician Chris Cornell (L) and daughter Toni attend 'The Promise' premiere during 2016 Toronto International Film Festival at Roy Thomson Hall on September 11, 2016 in Toronto, Canada. (Photo by Brian de Rivera Simon/WireImage)
TORONTO, ON - SEPTEMBER 10: Musician Chris Cornell (L) attends the Hollywood Foreign Press Association and InStyle's annual celebration of the Toronto International Film Festival at Windsor Arms Hotel on September 10, 2016 in Toronto, Canada. (Photo by George Pimentel/WireImage)
LOS ANGELES, CA - FEBRUARY 10: Musician Chris Cornell (R) and daughter Lily Cornell arrive at SAINT LAURENT At The Palladium at Hollywood Palladium on February 10, 2016 in Los Angeles, California. (Photo by Axelle/Bauer-Griffin/FilmMagic)
LOS ANGELES, CA - FEBRUARY 10: Musician Chris Cornell (R) attends Saint Laurent at the Palladium on February 10, 2016 in Los Angeles, California for the Saint Laurent Los Angeles show. (Photo by Stefanie Keenan/Getty Images for SAINT LAURENT)
LOS ANGELES, CA - FEBRUARY 10: Recording artist Chris Cornell attends Saint Laurent at the Palladium on February 10, 2016 in Los Angeles, California for the Saint Laurent Los Angeles show. (Photo by Stefanie Keenan/Getty Images for SAINT LAURENT)
MALIBU, CA - NOVEMBER 15: Musician Chris Cornell (L) and Toni Cornell attend Rock4EB! 2015 with Ed Sheeran and David Spade on November 15, 2015 in Malibu, California. (Photo by Todd Williamson/Getty Images for EB Kids)
NEW YORK, NY - DECEMBER 08: Chris Cornell and family attend the world premiere of Disney's 'Into the Woods' at Ziegfeld Theater on December 8, 2014 in New York City. (Photo by Taylor Hill/FilmMagic)
BEVERLY HILLS, CA - AUGUST 28: Singer Chris Cornell and his daughters arrive to the special screening of 'Tinker Bell And The Great Fairy Rescue' held at La Cienega Park on August 28, 2010 in Beverly Hills, California. (Photo by Barry King/FilmMagic)
HOLLYWOOD, CA - APRIL 11: Musician Chris Cornell (C) and family arrive at the premiere of Marvel Studios' 'The Avengers' at the El Capitan Theatre on April 11, 2012 in Hollywood, California. (Photo by Kevin Winter/Getty Images)
LOS ANGELES, CA - MARCH 8: (L-R) Chris Cornell, Toni Cornell and Vicky Cornell attend BRING YOUR HEART TO OUR HOUSE: JOHN VARVATOS partners with CONVERSE for the 7th ANNUAL STUART HOUSE BENEFIT at John Varvatos on March 8, 2009 in Los Angeles, California. (Photo by ANDREAS BRANCH/Patrick McMullan via Getty Images)
March 8, 2009 West Hollywood, Ca.; Chris Cornell,wife Vicky Karayiannis and children; John Varvatos 7th Annual Stuart House Benefit; Held at the John Varvatos Boutique (Photo by Gregg DeGuire/FilmMagic)
SEPTEMBER 5: Chris Cornell attends CONDE NAST MEDIA GROUP celebrates Fifth Anniversary of FASHION ROCKS red carpet arrivals at Radio City Music Hall on September 5, 2008 in New York City. (Photo by CHANCE YEH /Patrick McMullan via Getty Images)
LOS ANGELES, CA - FEBRUARY 18: (L-R) Daughter Toni Cornell and Chris Cornell sighting on February 18, 2009 in Los Angeles, California. (Photo by COP/BuzzFoto/FilmMagic)
Singer Chris Cornell and his daughter arrive at the Kennedy Center for the Kennedy Center Honors. (Photo by Ken Cedeno/Corbis via Getty Images)
BEVERLY HILLS, CA - MARCH 11: (L-R) Christopher Cornell, Chris Cornell, Toni Karayiannis and Vicky Cornell attend Hollywood and Fashion Support the 5th Annual John Varvatos Stuart House Benefit at Beverly Hills on March 11, 2007 in Beverly Hills, California. (Photo by Andreas Branch/Patrick McMullan via Getty Images)
WEST HOLLYWOOD, CA - MARCH 19: Musician Chris Cornell and his daughter attend the John Varvatos 4th Annual Stuart House Benefit at the John Varvatos Boutique on March 19, 2006 in West Hollywood, California. The Stuart House serves the special needs of child victims of sexual abuse. (Photo by David Livingston/Getty Images)
Chris Cornell arrives at Conde Nast Media Group's Fifth Annual Fashion Rocks at Radio City Music Hall on September 5, 2008 in New York City. (Photo by Kevin Mazur/WireImage)
Chris Cornell of Audioslave with daughter Toni Cornell (Photo by Jon Kopaloff/FilmMagic)