Simmons, who joins celebrity ambassadors including British soccer player David Beckham, tennis player Roger Federer and actress Angelina Jolie, was appointed as ambassador to honor past and present victims of slavery.
"Providing awareness is a key factor, there's ongoing suffering and new modern day slavery," Simmons told reporters at U.N. headquarters.
U.N. agencies have been trying to draw attention to human trafficking and the enslavement of women and children in the sex trade.
Goodwill ambassadors help focus attention on the work of the U.N. through public appearances.
Simmons co-founded Def Jam Records more than two decades ago before selling it in 1999. In 2005 he returned to work with the label, which was the original home to rap stars such as Run-DMC and Public Enemy.
(Reporting by Megan Davies; editing by Alan Elsner)
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