against AC Milan to qualify for the last eight 4-2 on aggregate, are widely considered favourites to win the trophy for the fourth time in eight seasons at Wembley in May.
PSG, who saw off Valencia in the last 16, believe however that this could be a turning point in their climb to the peak of the European game.
The wealthy French club, under experienced coach Carlo Ancelotti, are on course for their first domestic title for 18 years as well as being in the last eight of the Champions League after an 18-year absence.
They go into Tuesday's tie, however, as underdogs for the first time this season - and will do well to survive it.
Qatari fund QSI has set PSG a tough agenda of winning the Champions League within five years, having bought the club last year and poured huge amounts of money into transfers to build a team made for Europe.
Centre back Thiago Silva, front man Zlatan Ibrahimovic and forward Ezequiel Lavezzi, who all signed last year, have been key in helping PSG reach this stage, and at least they have a good omen on their side.
The last time they reached the quarter-finals in 1995, they beat Barcelona but much has changed since. PSG have been absent while Barcelona have been crowned European champions three times.
Thiago Silva said the tie was "the game we all were dreaming about" and the expensively purchased trio will have to raise their level to the heights if PSG are to stand any chance of winning.
Latest signing David Beckham, who joined them on a five-month deal in January, believes they can meet these expectations.
"This club have high aspirations. We want to go as far as we can in all competitions," the former England captain told reporters after the Ligue 1 home win over champions Montpellier on Friday.
"It's obvious that we have the players for it. There's no doubt we have the mentality. Now, it's up to us to prove it on the pitch.
"Or course, it will hard, but very exciting too," added Beckham.
PSG's chances were boosted when Ibrahimovic was freed to face his former club after the two-match ban imposed following his dismissal at Valencia was halved.
"It changes the deal," midfield Clement Chantome said.
Ibrahimovic had a mixed year-long spell at Barca but said facing them again would not pose any problems for him.
"I have already played against Barcelona since I left and the game will be special for everybody here," said the Swede, who faced his former team mates in the group stage with AC Milan in 2011.
"How to beat them is the question. We will need to stay focused and the coach will probably set up specific tactics to block the best team in the world."
While PSG will bank on Ancelotti's tactical expertise, his Barcelona counterpart Tito Vilanova could return to the dugout for the first time after two months in New York receiving cancer treatment during which his assistant Jordi Roura has been in charge.
Vilanova flew back to Barcelona last week and took training on Friday but did not travel with the side to Vigo on Saturday.
"The return of Tito re-energises the whole team," goalkeeper Jose Manuel Pinto said after their 2-2 draw at Celta Vigo.
The La Liga leaders maintained their 13-point advantage over Real Madrid at the top of the standings, with nine games left to play, but were disappointed to concede a late equaliser despite having fielded a weakened side.
World Player of the Year Lionel Messi set up the first and scored the second to complete a run of netting in 19 successive league games, against every team in La Liga consecutively.
Vilanova called up Jordi Alba and Xavi, who missed Saturday's game but have both recovered from hamstring strains they suffered while on international duty with Spain.
Captain Carles Puyol and Adriano Correia are out injured and, with forward Pedro suspended, Cristian Tello could feature in Paris. The pacy 21-year-old winger scored Barca's first against Celta and set up the second for Messi.
"Tello is an option," Roura said. "He is a player with a lot of talent who brings something different to the team. He is working well and gaining the aggression he lacked. Today he played an extraordinary game."
Paris St Germain: 30-Salvatore Sirigu; 26-Christophe Jallet, 2-Thiago Silva, 13-Alex, 17-Maxwell; 29-Lucas, 24-Marco Verratti, 14-Blaise Matuidi, 27-Javier Pastore; 18-Zlatan Ibrahimovic, 11-Ezequiel Lavezzi
Barcelona: 1-Victor Valdes; 2-Dani Alves, 3-Gerard Pique, 14-Javier Mascherano, 18-Jordi Alba; 16-Sergio Busquets, 6-Xavi, 8-Andres Iniesta; 4-Cesc Fabregas, 10-Lionel Messi, 7-David Villa.