The Brazil centre-back netted the 86th-minute equaliser that sent the match to extra-time, before Thiago Silva cancelled out Eden Hazard's 96th-minute penalty to take the score to 3-3 on aggregate and send PSG through.
The goals only tell half the story, though, with PSG star Zlatan Ibrahimovic controversially sent off in the first half before Gary Cahill put Chelsea ahead with nine minutes to go.
The modern-day etiquette is to not celebrate against a former club - Danny Welbeck incurred the wrath of some Manchester United fans following his winner for Arsenal at Old Trafford only on Monday - but Luiz, who was at Stamford Bridge from 2011 to 2014, did not hold back.
"My cycle finished in Chelsea, PSG gave me a great opportunity to continue my career," Luiz told Sky Sports 5. "I was very happy at Chelsea. I respect everyone.
"Tonight was good for me to score. I said I wouldn't celebrate but my emotions I couldn't control.
"Thank you to Chelsea and sorry I celebrated because I was so emotional."
"It is amazing for everyone, amazing for Paris club, for Paris city," he added. "We did a great game, we tried to win the game.
"I am happy to be in the next round but we have a long way to go to win the Champions League. We have to keep our feet on the floor."
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