Video! Justin Timberlake 'Sittin' on the Dock' with First Family

J.T. performed the Otis Redding hit with a little help from famed guitarist Steve Cropper, who co-wrote the song. The two were part of an A-list lineup that included Mavis Staples, Booker T. Jones, Ben Harper, the Alabama Shakes and "American Idol" alum Joshua Ledet. Al Green was unable to make it due to a bad back.

While Timberlake seemed calm and confident as he made jokes on stage and addressed the Commander-in-Chief mid-song -- "Mr. President, everybody, come on" -- his wife Jessica Biel, failed to contain her excitement. She tweeted with glee, "I hugged POTUS. I hugged POTUS. I hugged POTUS.”

Earlier in the day, Timberlake and several other artists participated in First Lady Michelle Obama's "Soulsville USA" student workshop. High school students from across the country traveled to the White House to learn about what Mrs. Obama called "the rhythmic groove of Memphis soul."

The “In Performance at the White House” series began during President Carter's administration in 1978 with the goal of celebrating American music. The “Memphis Soul” edition, focused on the city's mid-to-late 1960s tunes, will be the tenth “Performance” since Obama took office in 2009.