The 30-year-old former Portugal international had been linked with a move to the Estadio da Luz after gradually falling out of favour under Bernd Schuster and Javier Gracia in Andalusia.
He moves to the club on a two-year deal, with his contract including an option for a further season.
The left-back can also operate as a winger and will again link up with coach Jorge Jesus, who he worked under at Belenenses.
From there, he went on to spend time at Malaga and Lazio before returning to La Rosaleda for a second stint with the club.
"In these years I spent in Portugal and now Spain I evolved as a player and I want to continue," he told Benfica's official website.
"I'll now be trained by someone as passionate and tactical as Jorge Jesus."
Since winning the title last term, Benfica have been active in the transfer market with the likes of Victor Andrade and Luis Felipe arriving.
However, Jesus has lost quality players in the form of Ezequiel Garay, Lazar Markovic and Jan Oblak.