The Australian glided into the second round after hitting overdrive in the second set to sail past Mariano Navone, of Argentina, on Tuesday.
De Minaur, the No 9 seed, eased past Navone 7-5 6-1 to advance to a meeting with Miomir Kecmanovic, Serbia's lucky loser.
That came after one of his main rivals for a berth at the end-of-season finale in Italy, Andrey Rublev, hit the self-destruct button against Francisco Cerundolo.
Fellow Aussie Alexei Popyrin also had a good day, downing Mario Berrettini 7-5 7-6 (7-2) to set up a tie with fourth seed Daniil Medvedev.
The sixth-seeded Rublev lost two tiebreakers and his temper as his hopes of qualifying for the ATP Finals took a big hit.
Smooth sailing for Demon ⛵️— ATP Tour (@atptour) No. 9 seed @alexdeminaur will face lucky loser Kecmanovic in the second round in Bercy.#RolexParisMasters | @RolexPMasters pic.twitter.com/mM8WvmG2i4October 29, 2024
He eventually lost 7-6 (8-6) 7-6 (7-5) in a match that lasted more than two hours.
Rublev was so frustrated at one point in the second set that he smashed his racket against his left knee at least seven times in succession. Video footage showed the outburst left his knee bleeding.
The ATP said that Taylor Fritz became the fifth player to qualify on Tuesday, making it to the season-ending tournament for the second time in the past three years.
The indoor event gathering the top eight players of the season will take place in Turin, Italy, from November 10-17.
Fritz joins Jannik Sinner, Carlos Alcaraz, Alexander Zverev and Daniil Medvedev in the field.
Earlier on Tuesday, big-serving Giovanni Mpetshi Perricard of France hit 28 aces on his way to defeating Frances Tiafoe 6-7 (7-5) 7-6 (7-4) 6-3.
Fresh from winning the title in Basel, Mpetshi Perricard also had 13 double-faults but never dropped his serve against the 14th-seeded American player.
Mpetshi Perricard converted his sole break point to win his first match at a Masters 1000 tournament.
The Frenchman, who started the year ranked 200th, rose to a career-high ranking of No.31 on Monday.
According to ATP statistics, Mpetshi Perricard has served 512 aces in just 27 matches this season.
He will play Karen Khachanov, who overcame Australia's Christopher O'Connell 6-4 3-6 7-6 (8-6) in the second round.
On a good day for local players, Arthur Fils also progressed to the second round by edging Croatian Marin Cilic 7-6 (7-5) 6-4. He now meets Jan-Lennard Struff, who defeated Lorenzo Musetti 6-4 6-2.
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