PHOTO: AFP
A week on from their 2-2 draw in the French capital, City saw Sergio Aguero squander a first-half penalty after he had been felled by PSG goalkeeper Kevin Trapp, but De Bruyne's late strike settled the Etihad Stadium nerves and completed a 3-2 aggregate success.
Fifteen points off the pace in the Premier League and widely considered the tie's underdogs, City advance with hope intact that manager Manuel Pellegrini may yet bow out with a Champions League winner's medal around his neck before handing over to Pep Guardiola.
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"It's a very great achievement for the club, not only to be in the best four teams of Europe, but also in the style of play that we never change," said Pellegrini.
"Kevin De Bruyne is an important player for us. We deserved a goal before he scored. We dominated the game from the beginning until the end."
But it was a bitterly disappointing evening for PSG coach Laurent Blanc, who lost Thiago Motta to injury and has now seen his team eliminated in the quarter-finals four seasons in a row.
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The French champions' ambitious Qatari owners must once again content themselves with the pursuit of another domestic quadruple, while Zlatan Ibrahimovic, whose contract expires at the end of the season, may never grace the continental stage in their colours again.
"If we analyse the two matches, in our strong moments we weren't clinical enough," said Blanc.
"City were much more clinical and that's why they qualified. Bravo to them. They're a very good team -- not spectacular, but very effective."
The burst of sky-blue tickertape that greeted the teams as they entered the pitch illustrated the importance of the occasion to both clubs, while PSG's shape at kick-off confirmed pre-match reports that they would be set out in an untested 3-4-1-2 system.
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With Angel di Maria operating in a free role, PSG had plenty of options in midfield and they made an assured start, City goalkeeper Joe Hart forced to make a finger-tip save from a zinging Ibrahimovic free-kick.
But as City began to probe, so they exposed fissures in PSG's new-look defence and after Aguero had twice shot wide, a loose pass from auxiliary right-sided centre-back Serge Aurier allowed Fernandinho to set Aguero clear.
Sliding out, Trapp felled the Argentina striker with his feet, but the presence of two covering defenders meant that he was only booked and from the penalty, Aguero placed the ball a foot wide of the right-hand post.
It was a let-off for the visitors, but after another careless Aurier pass had allowed Jesus Navas to curl wide, they suffered a further blow when Motta went off holding the back of his left thigh.
With Blaise Matuidi suspended and Marco Verratti injured, it left PSG without their entire first-choice midfield and Blanc promptly rejigged, sending on Lucas Moura and reverting to his trusted 4-3-3.
Although City, gamely, continued to push in search of a goal that would have given them an outright lead, PSG began to knock on the door at the other end.
Hart had to parry another stinging Ibrahimovic free-kick and then clubbed the ball over his crossbar after Thiago Silva's header from a Lucas corner spat up off the turf towards him.
The introduction of Javier Pastore for the hapless Aurier, on the hour, left PSG with their full attacking armada on show, but it was De Bruyne who stole the headlines, brilliantly shaping a right-foot shot into the bottom-right corner from outside the box to crush PSG's spirit.
City's fans had to endure a couple more nervous moments, with Hart rushing out superbly to save from Edinson Cavani and Ibrahimovic seeing a goal ruled out for offside, before the final whistle rubber-stamped their club's arrival in the European big-time.
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