Piastri rose from fourth on the grid to the race lead, forcing Verstappen into a mistake to spring clear of the pack.
Lando Norris finished second after dropping down the order after he came off second-best after an opening corner tussle with Verstappen.
The Dutchman ultimately slipped to fourth after a mid-race Virtual Safety Car helped George Russell jump the Red Bull for third during the pit cycle.
Verstappen swept across the road to cover off from Norris, only to run wide, which allowed the McLaren driver to challenge on the exit of the first corner.
The pole-sitter’s slow exit also allowed Piastri to buy in, with Kimi Antonelli joining the battle at the front, moving up to second in the opening exchanges as Norris was left the road at Turn 2 and dropped back.
Antonelli then briefly challenged Verstappen before the Dutchman established himself in the lead with Piastri third as Norris fell behind Alex Albon to sixth after running off the road at Turn 2.
Norris and Verstappen had made contact as Jack Doohan reported a puncture and attempted to limp his way back to the pits, but ultimately had to stop on track.
A mistake from Antonelli into Turn 1 on Lap 2 saw him drop back from Verstappen and into the clutches of Piastri before a Virtual Safety Car was deployed for Doohan’s stricken Alpine.
The Australian made heavy contact with Liam Lawson as they pinched on the apex of Turn 2, launching the Racing Bulls into the air as Doohan’s left-front tyre was peeled from the rim.
When racing resumed, Piastri pounced to claim second off Antonelli into Turn 11 on Lap 4.
It was a decisive move, claiming the inside line and with it the place from his young Mercedes rival.
After five laps, the order was Verstappen from Piastri, Antonelli, George Russell, Norris, Carlos Sainz, Albon, Charles Leclerc, Yuki Tsunoda, and Esteban Ocon.
A good run out of the first corner on Lap 7 saw Norris pinch fourth from Russell.
The McLaren driver shadowed the Mercedes driver before surprising the Brit with a move into Turn 4.
Russell was struggling, his hard compound tyres not offering the grip of the mediums of those around him.
As such, he quickly fell back into the clutches of Sainz, who had Albon and Leclerc for company.
On Lap 9, Norris passed Antonelli at the same spot Piastri had earlier in the race.
Ahead, the Australian had latched onto the gearbox of the leader, forcing Verstappen to defend into Turn 11 and Turn 17 on Lap 11.
The scrap continued into the first turn on the next lap as the Dutchman again moved to cover the inside line.
Half a lap later, Piastri looked to go around the outside at Turn 12, only to be walked wide and back out of the move.
As they started Lap 14, Piastri finally forced the mistake and took the lead.
A better run out of Turn 17 allowed him to draw alongside Verstappen, who moved to the inside but braked too late into Turn 1.
That opened the door for Piastri to easily move through as Norris zeroed in on the Red Bull.
It was almost a repeat of Piastri’s pass on Lap 15, but Verstappen was able to hit his marks before opening the steering on exit to force the McLaren to back out as they entered Turn 2.
On Lap 17, Norris attacked into Turn 11, storming up the inside to slide wide, running off the road as he passed Verstappen.
Realising that, he quickly handed the spot back on the run to Turn 17 before finally making the move stick into Turn 11 on Lap 18.
Out front, Piastri had cleared out to the tune of nine seconds as he showed McLaren’s clear pace advantage.
Mercedes pitted Antonelli after 25 laps in an attempt to undercut Verstappen ahead.
However, a delay exiting the box hampered those chances and Red Bull covered that threat by pitting next time around.
A problem for Oliver Bearman as he started Lap 28 saw the Haas driver slow just as both Piastri and Norris passed the pit entry.
That triggered a second Virtual Safety Car that was perfectly timed for Lewis Hamilton, who was able to get into the lane.
Having completed a full lap under the Virtual Safety Car, McLaren called Piastri into the lane.
Norris followed him in, the 11.5s gap between them allowing the pair to double stack without issue.
Russell also boxed, rejoining as the Virtual Safety Car ended.
He still managed to get back on track ahead of Verstappen to take third place.
It left the order Piastri from Norris, Russell, Verstappen, Albon, Antonelli, Sainz, Leclerc, Hamilton, and Nico Hulkenberg, the German yet to stop after 33 laps.
A third Virtual Safety Car was triggered when Gabriel Bortoleto stopped on the back straight.
He’d pulled off to drivers’ left and was well off the racing line, the Brazilian having reported issues a handful of laps earlier.
It worked out poorly for Sainz as the Virtual Safety Car ended, Leclerc drawing alongside his former teammate.
Having run side by side for three corners, the Williams was finally elbowed aside into Turn 1, a move that also allowed Hamilton to steal a place as Sainz dropped two positions in one corner.
Ferrari then swapped Leclerc and Hamilton, the latter on the medium compound tyres and having lost time tucked up behind his teammate, much to the seven-time champion’s frustration.
The rain that threatened the circuit soon after abated, without impacting the race, as Piastri enjoyed a comfortable advantage over Norris.
The Australian managed a six-second lead for the remainder of the race to win from Norris, who’d reduced the gap by the chequered flag as the Australian extended his championship advantage.
Russell held on to a distant third despite pressure from Verstappen in the final laps, while Albon claimed fifth from Antonelli, Leclerc, Hamilton, Ferrari having reversed the pair once more inside the final five laps, with Sainz and Yuki Tsunoda rounding out the top 10.
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