The Brazil defender was unable to get out of the way of a Marco Verratti free-kick and saw the ball go past a helpless Petr Cech.
PSG took control of the game early on when Ezequiel Lavezzi scored after just three minutes.
But Chelsea got themselves back in the game thanks to an Eden Hazard penalty after Oscar was brought down in the area by Thiago Silva.
But with Chelsea dreaming of a draw to take back to Stamford Bridge next week, Luiz bundled the ball into his own net and then with the whistle about to go, Pastore pounced to make it 3-1 to the French champions to give Mourinho's men plenty of work to do in London.
Not in the plan: John Terry, David Luiz, Petr Cech and Cesar Azpilicueta look dejected after Chelsea concede a second
Oh no! Luiz can't get out of the way of the ball as it hits him and goes in
Back of the net: Luiz ends up in the goal along with the ball after PSG go 2-1 up
Pile driver: Ezequiel Lavezzi smashes home the opening goal against Chelsea
Off he goes: Lavezzi runs off in celebration as Branislav Ivanovic lies on the floor
Dream start: Lavezzi celebrates giving PSG an early lead
All together now: Lavezzi is mobbed by his teammates after his opening goal
From despair to where? Oscar and Andre Schurrle are shocked by the early goal
Firm punch: Petr Cech gets to the ball ahead of PSG defender Thiago Silva
Eyes on the ball: Christophe Jallet shields the ball from Chelsea's Cesar Azpilicueta
Not happy: Jose Mourinho protests on the touchline
Up for the challenge: Hazard takes the ball past the sliding tackle of Jallet
Keeping an eye on things: Brazil head coach, and
former Chelsea manager, Luiz Felipe Scolari keeps an eye on the
Brazilian contingent
Spot on: Eden Hazard levels the tie with a goal from the penalty spot
Going the wrong way: Hazard puts the ball past Salvatore Sirigu
Back on terms: Chelsea's players celebrate after Hazard makes it 1-1
Joy and despair: Hazard celebrates with team-mates after scoring as Zlatan Ibrahimovic looks dejected
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