On a night that will be remembered for some comical defending and a Zlatan Ibrahimovic penalty that was saved by City goalkeeper Joe Hart, the Premier League side twice punished mistakes by their hosts.
De Bruyne put City ahead on 38 minutes, only for Ibrahimovic to level after an embarrassing mix-up in the visitors' defence soon after.
Adrien Rabiot then put PSG ahead just before the hour, but Fernandinho made it 2-2 on 72 minutes and ensured the French giants will be chasing the tie in next Tuesday's second leg.
"It's up to us to make the away goals count. We are making history for the club and we don't want it to end."
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City were appearing at this stage for the first time and were handicapped by the absences of injured captain Vincent Kompany, Yaya Toure and Raheem Sterling.
However, Hart had recovered from injury in time to play and De Bruyne started after making his own comeback from two months on the sidelines at the weekend, giving the English side's attack a fearsome look to it.
The home support were furious soon after when Serbian referee Milorad Mazic refused to give Paris a penalty after Blaise Matuidi went down in the box under pressure from Eliaquim Mangala, but PSG did win a spot-kick in the 13th minute for a foul by Bacary Sagna on Luiz.
Perhaps the 34-year-old Swede was feeling the pressure in what could be his last chance to win the Champions League, because he passed up another huge opportunity midway through the first half, blazing over the bar after a Thiago Motta pass had split the away defence.
Fernandinho intercepted a Matuidi pass intended for Rabiot and advanced towards the edge of the box before teeing up De Bruyne, who took a touch and fired past Kevin Trapp.
- Horror moment -
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However, City inexplicably gifted the French champions an equaliser only three minutes later.
It was a horror moment for Hart and Fernando, with the goalkeeper choosing to play a goal-kick short to the Brazilian-born midfielder on the edge of the area despite Ibrahimovic lurking in close proximity.
PSG came out in the second half with the momentum after that and they took the lead on 59 minutes thanks to one-time City youth player Rabiot.
Edinson Cavani turned a corner towards goal and Hart saved, but the ball fell kindly for Rabiot to tap in.
PSG sensed a chance to increase their advantage before the second leg and a Di Maria cross from the right was headed against the woodwork by Ibrahimovic.
Instead City pounced on some more comical defending to grab a second away goal, Fernandinho gleefully prodding into the net after neither Serge Aurier nor Thiago Silva were able to clear a low ball into the box from the away right.