Justin Timberlake, Miley Cyrus and Charlize Theron were among the celebrities who appeared at the fifth annual Fashion Rocks concert celebrating the relationship between music and fashion. They walked the red carpet Friday night at Radio City Music Hall amid a media circus angling for glamour shots of other stars including Fergie, Rihanna, Chris Brown and the “Gossip Girl” gang. Brown, the R&B heartthrob, soaked up all the attention with a smile as he showed off his dapper ensemble of a black vest and shirt, gray pants, shiny shoes and diamond stud earrings. “To be a musician and a great entertainer, you have to be a trendsetter. To be a trendsetter, you have to know fashion — and I have fun with it,” explained the singer, who later changed into khakis and a black shirt and scarf for a performance of his hit song “Forever.” The event will air Tuesday in a two-hour special on CBS. Proceeds will benefit Stand Up To Cancer, a program established by the Entertainment Industry Foundation to raise money for cancer research. Stand Up To Cancer held a live telethon that aired simultaneously on ABC, NBC and CBS on Friday night … Other performers included Timberlake, Kid Rock, Keith Urban, Duffy, the Pussycat Dolls and the Black Eyed Peas. A highlight was Timberlake and Beyonce’s sizzling duet of “Ain’t Nothing Like the Real Thing,” which channeled the soulful sound of the classic song’s original singers, Marvin Gaye and Tammi Terrell. Stars mingled and sipped cocktails backstage in the green room, where Leighton Meester of the CW teen drama “Gossip Girl” and her actor-beau Sebastian Stan hung out before she introduced Duffy’s performance of “Mercy.” Meester’s “Gossip” co-star Chace Crawford chatted up actress Hayden Panettiere, who embraced her rock-star side in a silver Ferragamo minidress and black heels. “I usually try to mix class and then really funk it out,” Panettiere said of her personal style. “It’s rock meets class. I try — not always succeed, but I try.”

Wow, this really does sound like a star-studded event … I can’t wait to check it out when it airs on Tuesday night. I understand there were some very cool performances, including one from Rihanna that I will be talking about in a bit. After the jump, check out some pics of Beyoncé, Mariah Carey, Kid Rock and others as they took to the stage last night …

Oh yeah, by the looks of it Conde Nast really managed to pull in the big guns for this event. Again, this show looks like it is not to be missed. I know I’ll be tuning in Tuesday night.

[Photo credit: Splash News, Wireimage; Source]