The Portuguese international faced tough competition at Camp Nou last season with Catalan legend Luis Enrique often preferred in the right wing berth.
Benfica want to lure the 21-year-old former Sporting Lisbon star to the Estadio da Luz and may tempt the Spanish giants with a swap deal involving highly-rated Angolan striker Pedro Mantorras.
Simao is valued at around £10 million by Barca and Benfica would probably have to offer Mantorras and £5 million to secure the services of the player.
