Laurent Blanc's men will look to maintain their strong record against Portuguese opposition when last season's Europa League finalist visits.
On matchday one, PSG thumped Olympiakos 4-1 in Greece and Benfica sealed a comfortable 2-0 success at home to Anderlecht, so a win for either side will open up a three-point gap and edge the winner closer to the knockout stages.
Last season saw les Parisiens eliminated in the quarterfinals by Barcelona on away goals, while Benfica came third in a group containing the Spanish giant and Celtic before going on a run to the Europa League final, where the club was beaten 2-1 by Chelsea.
The two sides last met two years ago in the Europa League round of 16 in 2010-11, with Benfica winning 3-2 on aggregate.
The only other meetings between the teams came in the same round of the same competition in 2007, and again the Portuguese outfit came out on top, overturning a 2-1 first-leg deficit with a 3-1 victory in Lisbon.
PSG has never lost a home fixture to Portuguese opposition, winning four and drawing two, and Laurent Blanc's side comes into the game full of confidence having yet to taste defeat in Ligue 1 this season.
As reigning French champion, PSG is currently only denied top spot by Monaco on goal difference, having taken five wins and three draws from the club's opening eight fixtures, conceding just four goals in the process. PSG defeated Toulouse 2-0 on Saturday at the Parc des Princes, with goals from Marquinhos and Edinson Cavani.
Blanc will be without talismanic defender Thiago Silva, who pulled up with a hamstring injury during the 1-1 draw with Monaco earlier this month and is facing six weeks out of action.
Benfica, two-time European champion, has a good recent record against French opposition, with last season's 3-2 victory in Bordeaux in the Europa League making it four wins in the last five games against Ligue 1 sides.
Domestically, Benfica finds itself five points adrift of Porto after losing further ground at the weekend following a 1-1 home draw with Belenenses.
Bruno Cortez and Nicolas Gaitan both returned from injury in that game so coach Jorge Jesus will have them available as Benfica looks to emulate Bayern Munich’s feat in 2012 by reaching the Champions League final in its own stadium.