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The 'I Just Call You Mine' singer is scheduled to make a duet with Train's frontman Pat Monahan to provide a theme song for the live wedding ceremony.
Kenny Chesney is the biggest nominations gatherer this year while Taylor Swift is the only woman in the Entertainer of the Year race.
Along with guest performers like Mary J. Blige, OneRepublic, Gavin DeGraw and Christina Perri, Bieber serenades a number of foster kids in a festive TV special.
While most of the big stars attending the benefit event opt to go casual with T-shirt and denims, Leona Lewis and Katie Couric choose more formal outfit.
Out of five remaining categories, Miranda Lambert has her name appearing in four, including the top honor Entertainer of the Year.
Sandra Bullock also showed off some singing skills, delivering a few bars of Deep Purple's 'Smoke on the Water' before introducing Faith Hill's performance.
Miley Cyrus sings 'Party in the U.S.A', Leona Lewis performs 'Happy', and Kelly Clarkson delivers 'Already Gone' at the Brooklyn Academy of Music (BAM) Howard Gilman Opera House.
Miley Cyrus gets Sheryl Crow as her duet partner, Jennifer Hudson has Stevie Wonder as her collaborator, while Leona Lewis will take the stage with Cyndi Lauper.
Brad Paisley receives six nominations, while Keith Urban, Jamey Johnson, George Strait, Taylor Swift and Zac Brown Band get four each.
Taylor Swift and T-Pain will make a duet performance at this year's CMT Music Awards at Nashville's Sommet Center on June 16.
Sugarland got five nominations at this year's Country Music Television Awards, while Brad Paisley and Taylor Swift followed with four gongs each.
Presenters for 2009 ACM Awards are varied from country music band Rascal Flatts and R&B/soul singer Jamie Foxx to actress Jennifer Love Hewitt and supermodel Marisa Miller.