The former Leeds winger opened the scoring just before half-time, but PSG hit back with two goals in two minutes just after the break.
Ousmane Dembele equalised against his old club before Vitinha’s effort rocked the Spanish giants.
Luis Enrique’s Ligue 1 hosts hit the woodwork either side of Raphinha’s equaliser midway through the second period.
And Andreas Christensen settled an engrossing encounter between two heavyweight clubs with a close-range header 13 minutes from time.
Kylian Mbappe was largely subdued as his quest to become a European champion before leaving the French capital in the summer suffered a setback.
Sebastien Haller’s late goal gave Borussia Dortmund a lifeline as they lost 2-1 against Atletico Madrid in Spain in the night’s other tie.
Atletico took early charge with Rodrigo de Paul scoring after just four minutes, and it looked bleak for Dortmund when Samuel Lino added a second in the 32nd minute.
But Haller struck nine minutes from the end to set up an intriguing second leg in Germany, although it could have been even better for Dortmund as Julian Brandt’s stoppage-time header came crashing back off the crossbar.