The Uruguay international left Liverpool for Barcelona last year in a £75 million ($114.3 million, 103.7 million euros) deal after scoring 82 goals for the club in 133 appearances during a three-and-a-half-year spell.
He is one of several players who will feature in a game being organised by the Liverpool FC Foundation that will see captain Steven Gerrard and former defender Jamie Carragher each captain a team they have selected.
Former Liverpool favourites Fernando Torres, Pepe Reina, Dirk Kuyt and Xabi Alonso will also return to Anfield for the March 29 fixture, as well as players including Thierry Henry, John Terry and Didier Drogba.