Williams is featured on the title track, which is also produced by the 'Happy' singer, reported MTV online.
"We have definitely decided on 'Paperwork' featuring Pharrell [because it] pretty much sums up the tone of the album. The cinematic presence of it all," said TI, whose real name is Clifford Joseph Harris, Jr.
"When you listen to the album, top to bottom, it kinda sounds like the score to a movie and I think 'Paperwork' is the perfect introduction to that," he added.
'No Mediocre' featuring Azalea - who is signed to TI's record label Grand Hustle - was released as the lead single from the album.
Paperwork: The Motion Picture is a follow-up to the rapper's 2012 album Trouble Man: Heavy Is the Head, which was recorded after his release from prison in August 2011.