Former Brazilian international Luisão, who spent 14 years at the Lisbon club, is said to be packing his bags for the West Midlands and is expected to be ready to take the field this weekend for the short trip south to St Andrews to face Birmingham City should Wolves manager Wlater Zenga require his services.
Luisão, who is 35, agreed to terms following a meeting Benfica chairman Luis Filipe Vieira is said to have had in London with his Wolves counterpart.
Reports by daily newsaper Jornal de Notícias and sports daily Record claim Luisão, which is literally translated as 'Big Luís', has signed a two year deal.
The towering central defender is expected to be on a deal that will see him earn around £35,000 or €40,000 a week at Molineux.