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Fallon will host the episode and Timberlake will serve as musical guest, while Paul Rudd and John Goodman are tapped as the hosts for other episodes next month.
The 'Mirrors' singer covers one of the five GQ Men of the Year issues, saying in accompanying interview, 'I don't see myself as someone who's ever going to be defined by one moment.'
Joining the likes of Miley Cyrus, Lady GaGa, Imagine Dragon and One Direction, the 'Mirrors' singer will make his first appearance at the annual awards show as a solo artist.
The designer has exclusively created 600 pieces that include eight custom-made outfits for the pop star and original pieces for all the backup dancers, band members and vocalists.
The Canadian singer will join the former NSYNC member at six shows, which will take place in Brooklyn, Hartford, East Rutherford, Philadelphia, Raleigh, and Nashville.
The Ryan Reichenfeld-directed sees Timberlake trying to fix his relationship with his on-screen girlfriend, who is played by Riley Keough.
Giving Timberlake his second No. 1 album on the chart this year, the second installment of 'The 20/20 Experience' sells 350,000 copies in its first week.
The former member of NSYNC also performs 'True Blood', a track off his newly-released album, and an acoustic version of 2006's 'What Goes Around... Comes Around'.
The 'Late Night' show's host and the 'Runner, Runner' actor use hashtags for almost every phrase during their conversation before Questlove tells them, 'hashtag shut the f**k up.'
The former NSYNC member performs his hits, which include 'Cry Me a River', 'Rock Your Body', 'Mirrors' and singles off his upcoming 'The 20/20 Experience - 2 of 2' album.
Eleven songs from the second installment of chart-topping 'The 20/20 Experience' is available for streaming on iTunes one week ahead of its official release date on September 30.
The former NSYNC member performs 'TKO', 'True Blood' and 'Only When I Walk Away', three new tracks off his upcoming 'The 20/20 Experience - 2 of 2' album.
The track features Timberlake singing about wanting back a girl from his past whom he thinks he's already got over.
After slightly arguing about a man-purse, the 'Suit and Tie' singer and the 'Today' anchor get hitched in Las Vegas in their short funny skit.
The former member of NSYNC also reveals that he will debut new songs off his upcoming new record at iHeartRadio Festival, which will be held in Las Vegas.