The French giants showcased their attacking flair to overturn an early deficit and hand Villa their first defeat in eight matches across all competitions.
The Villans stunned the home crowd on 35 minutes when Morgan Rogers fired them ahead. John McGinn sparked the move, winning possession and feeding Marcus Rashford, who set up Youri Tielemans to deliver a pinpoint cross for Rogers to convert.
But PSG's response was swift and ruthless. Just before half-time, Desire Doue weaved through Villa's defence and unleashed a thunderbolt into the top corner to level the score.
After the break, PSG cranked up the pressure. Khvicha Kvaratskhelia put them in front, dancing past Axel Disasi and smashing the ball into the roof of the net.
Nuno Mendes sealed the win late on, latching onto Ousmane Dembele's through ball, twisting past his marker, and slotting home to spark wild celebrations.
Luis Enrique, PSG's head coach, hailed his team's resilience and superiority. "When a team scores without really creating chances, it's tough, but we've faced this before," he said.
"The result shows the gap between us and them, plus our fighting spirit. Football isn't always fair, but we stick to our strengths." Looking ahead to the second leg, Enrique added, "We don't play to sit back or calculate. We're going there to win, that's our DNA."
Unai Emery, facing his former club PSG for the first time as Villa's boss, had urged his side to frustrate the hosts early on. While they held firm for spells, Emiliano Martinez denying Vitinha and Dembele.
Villa couldn't withstand PSG's relentless waves of attack. Emery admitted post-match, "They're a top side, and we knew it'd be a battle. We've got work to do at home."
Recent updates from PSG's official X account confirm their confidence, with a post declaring, "Two-goal lead, but we're not done yet, onto Villa Park!" Meanwhile, Villa's Rogers took to X, vowing, "We'll fight back in the return leg. This tie's far from over."
With a two-goal cushion, PSG are firmly in the driving seat as they eye a semi-final spot, while Villa face an uphill climb to turn the tide at home.