The Greek champions were eliminated at the group stage in the 2012/13 competition, just one point adrift of second-placed Arsenal, despite claiming three victories in their six games.
This year presents a good opportunity for Olympiacos to progress because, while PSG are the stand-out team in Group B, Benfica and Anderlecht are beatable opposition.
Striker Javier Saviola joined Olympiacos in July and he knows the magnitude of the challenge they will face on Tuesday.
He told the club's official website: "It will be a very difficult game.
"Paris is a team that always wants to win, they are very strong offensively, playing attacking football with high-level players .
"But I believe that we have the right weapons to tackle a difficult and important game.
"I think we are well prepared and what remains is to be psychologically ready to deal with a team of the quality of PSG."
While Saviola has plenty of European experience, it will be his first Champions League game at the Karaiskakis.
"I do not know exactly what to expect," he said. "I know it will be a very special night.
"Olympiacos is known for a world that always tries to impart strength and support the team."
PSG arrive in Piraeus third in their domestic league and on the back of three straight wins.
They were agonisingly close to qualifying for the Champions League semi-finals last season, going out to Barcelona on away goals in the last eight after both games were drawn.
Lucas Moura scored the second in PSG's win against Bordeaux at the weekend and although he acknowledged his side are perceived to be favourites, the Brazil forward was taking nothing for granted.
He told the club's official website: "There are no easy teams in the Champions League, even if we face teams assumed to be weaker than us.
"We can not assume that it will be easy because everyone wants to win the Champions League.
"We will play every game like a final and climb the steps one by one...we will fight to be champions of Europe. "