The Group C clash in Lisbon gives Benfica the perfect chance to respond to a disappointing 3-0 defeat in their previous Champions League fixture.
Jorge Jesus’ men, beaten finalists in the UEFA Europa League last season, were humbled in the French capital.
Zlatan Ibrahimovic scored twice in the first 30 minutes, while Marquinhos also scored an early goal as the Ligue 1 champions cruised to victory.
Benfica are unlikely to be the only side taught a lesson by PSG this season, but the manner of the defeat will have dented their pride.
The Portuguese outfit opened their Champions League campaign with a 2-0 home win over Anderlecht and will hope to translate some of their recent league form into Europe's premier club competition.
After a slow start, Benfica have won three of their last four league fixtures and climbed to third in the Portuguese top flight.
However, strikers Miralej Sulejmani and Lazar Markovic are both struggling with thigh problems and Jesus has other injury problems to contend with.
Rodrigo has missed plenty of football while fellow knee injury victim Eduardo Salvio is not expected to return in 2013.
Olympiacos followed up a 4-1 home Champions League loss to PSG with a convincing 3-0 win at Anderlecht as Kostas Mitroglou netted a memorable hat-trick.
Incredibly, Mitroglou has scored three times in four different games this season and boasts 13 goals for his club in all competitions.
He was on target in a 4-1 win Greek Super League win at Platanias on Saturday, a result that saw Olympiacos remain top of the table.
Mitroglou is now third in Olympiacos' all-time European scoring standings, with 12 goals, and Greece manager Fernando Santos has urged the Portuguese public to take the chance to watch the in-form striker.
Santos said: "Go to 'Da Luz' to watch him play against Benfica. He has an uncanny ability of sensing goalscoring opportunities. It's not easy to find a player with his characteristics."
Olympiacos have gone 27 games without a draw in European competition, a run dating back to August 2009, while goalkeeper Roberto has saved a penalty in each of their two group fixtures this season.
Gaetan Bong (groin), Holebas (quadriceps) and Machado (knee) are all likely to miss the trip to Portugal, but Olympiacos can take heart from their terrific league form as they seek to cause another upset on the road.
