The Blues face an uphill task in overturning a 3-1 first-leg deficit but may be boosted by the return of Samuel Eto'o to spearhead the attack.
A late goal from Javier Pastore appears to have put the game out of the Blues' reach, but Jose Mourinho will hope his side can evoke the memories of their 2012 Champions League-winning campaign, when they turned around the same deficit against Napoli with a stunning 4-1 win after extra-time to secure a quarter-final berth.
Mourinho's side must score at least two goals to progress to the final four this time around, but they face a PSG side who are arguably held in higher regard than that Napoli side.
Goals from Ezequiel Lavezzi, a David Luiz own-goal and Pastore's individual effort rendered Eden Hazard's first-half penalty relatively meaningless, but it could yet make all the difference in the final reckoning.
Chelsea will undoubtedly be boosted by the absence of PSG's top scorer and talisman Zlatan Ibrahimovic but face injury problems of their own, with Ramires suspended, Nemanja Matic and Mohamed Salah ineligible and John Obi Mikel struggling with injury.
Mourinho will be forced to field Luiz in defensive midfield once more, while PSG's problems are on a lesser scale given Ibrahimovic's replacement will be to push Edinson Cavani infield into his favoured striker position.
Here are the three key battles for this evening's game...
Ezequiel Lavezzi v Branislav Ivanovic
The Argentine was key to Napoli's win over Chelsea in the first leg two seasons ago, notching two goals in the opening match.
He did not have quite the same impact at Stamford Bridge and neither did Cavani, who also scored against the Blues in the Stadio San Paolo, but Lavezzi has already spoken of how the French outfit will not repeat the mistakes made by his former side.
Ivanovic will be in for a tough evening against the 28-year-old, whose pace, trickery and movement cause Chelsea endless problems in the first leg. The Serb, who struck the all-important winner against Napoli in 2012, will have to be careful not to leave too much space in behind when he advances forward.
David Luiz v Blaise Matuidi
The Brazilian will be tasked with containing PSG's three-pronged midfield unit, which comprises of a variety of midfield talents.
While Thiago Motta provides the physical presence at the heart of the midfield, Marco Verratti pulls the strings with his accomplished passing game and then there's Matuidi, the engine of the trio.
His incessant midfield running and timing of his surges from deep are reminiscent of Luiz's midfield partner, Frank Lampard, in his pomp. With Lampard needed to provide a further dimension in the PSG half, Luiz will have to show discipline and responsibility to prevent his side from becoming outnumbered.
Samuel Eto'o v Alex
The suggestions are that Mourinho will gamble on the Cameroonian's fitness and field him from the start this evening, with Fernando Torres' continued toils in front of goal only serving to underling Chelsea's lack of a truly world class centre forward.
The closest they have to that at present is Eto'o and, after the failed experiment of playing Andre Schürrle at the tip of the frontline in Paris last week, it is important that Eto'o is fit and firing this evening.
He has the ability to drag players out of position and open up space for the likely triumvirate of Eden Hazard, Oscar and Willian in behind him and will fancy his chances up against the ageing Alex, even if Thiago Silva represents a daunting prospect to overcome at the heart of the PSG defence.