But PSG dominated the second half and scored a deserved equaliser when Edinson Cavani headed in.
Cavani came close to scoring a winner but prodded his effort wide after swapping passes with Blaise Matuidi.
Chelsea progressed at PSG's expense in last season's quarter-finals when they won on away goals after it finished 3-3 on aggregate.
They lost the first leg 3-1 in Paris last season but withstood long periods of pressure to ensure they return to Stamford Bridge on 11 March with a slight advantage thanks to the away goal.
David Luiz moved from Chelsea to PSG in the summer and performed well against his former club in midfield.
Luiz was occasionally used in that position by Mourinho during his time at Stamford Bridge but had not previously played there for PSG.
With Luiz holding, Matuidi was free to stride forward and Thibaut Courtois, returning in place of Petr Cech, was forced into making saves in quick succession from the French midfielder and Zlatan Ibrahimovic.
Thiago Silva's headed clearance went out to Terry and the Chelsea captain's cross was flicked on by fellow centre-back Cahill for Ivanovic to steer his header beyond Salvatore Sirigu.
It was Ivanovic's fifth goal of the season but first in Europe since his winner against Benfica in the 2013 Europa League final.
PSG started the second half strongly and took advantage of poor marking from the visitors to equalise. Maxwell's pass freed Matuidi in the left channel and his cross was perfect for Cavani, who found space between Terry and Cahill to head the ball down and into the net.
The home fans were buoyant and Laurent Blanc's team pressed for a second.
They came close when Ibrahimovic tricked his way into a shooting position but Courtois again saved well and Ezequiel Lavezzi's follow-up was goal-bound until it hit Cesar Azpilicueta in the six-yard box.
Chelsea continued to look vulnerable on crosses and Luiz came close to scoring against his former employers when Courtois tipped his header over from Lavezzi's free-kick.
Cavani could have ensured Blanc's team travelled to London with a slender lead but prodded his shot wide after swapping passes with Matuidi.
And Chelsea were indebted to Courtois again in stoppage-time when he pushed over Ibrahimovic's powerful downward header.
Lineup, Bookings (4) & Substitutions (4)
Paris Saint Germain
- 30 Sirigu
- 23 Van der Wiel Booked
- 05 Marquinhos
- 02 Thiago Silva
- 17 Maxwell
- 24 Verratti Booked
- 32 David Luiz
- 14 Matuidi
- 22 Lavezzi (Pastore - 81' )
- 10 Ibrahimovic
- 09 Cavani
Substitutes
- 01 Douchez
- 06 Camara
- 15 Bahebeck
- 21 Digne
- 25 Rabiot
- 27 Pastore
- 34 Kimpembe
Chelsea
- 13 Courtois
- 02 Ivanovic Booked
- 24 Cahill
- 26 Terry
- 28 Azpilicueta
- 07 Ramires
- 21 Matic
- 22 Willian (Cuadrado - 79' )
- 04 Fàbregas Booked (Oscar - 83' )
- 10 Hazard
- 19 Diego Costa (Remy - 81' )
Substitutes
- 01 Cech
- 03 Filipe Luis
- 05 Zouma
- 08 Oscar
- 11 Drogba
- 18 Remy
- 23 Cuadrado
Ref: Cüneyt Çakir
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