Dutchman Verstappen, who has won the last four world titles, will start on the front row alongside Lando Norris who was just ahead of his McLaren teammate and championship leader Oscar Piastri.
Having led for much of Q3, Verstappen snatched back first place in the final seconds of qualifying from Norris, who has been strong this weekend and seemed to have pipped the Red Bull man at the last.
Verstappen completed his record-breaking lap in one minute and 18.792 seconds to beat the previous benchmark set by Lewis Hamilton at Monza in 2020 for Mercedes by 0.095s.
Verstappen was 0.077s ahead of Norris -- who also bettered Hamilton's previous record -- and 0.190s faster than Piastri, who leads Norris by 34 points at the top of the drivers' standings.
"I think that final lap was pretty decent, and to get pole here for us, I think, is big as it's not always been a good track for us," Verstappen told reporters.
However Verstappen, who trails Piastri by 104 points, will have both McLaren cars chasing him down from the green light on Sunday, an ominous prospect given that the British team have won 12 of this year's 15 GPs.
"Difficult to say," said Verstappen when asked about his chances in the race.
"I think this season so far, the race has not always been great. I hope that I can do something tomorrow, but I think it's been a great day for us."
Norris' second place came after he almost missed a top 10 spot on the grid, as he sat 11th before his final lap of Q2 sent him through with no time to spare.
McLaren lurking
And although he was unhappy with his qualifying performance, saying that he hit "every kerb possible", Norris seemed confident that either he or Piastri could overhaul Verstappen at the "Temple of Speed".
"I would definitely want to expect that. Everyone knows that our race pace is probably the biggest strength... We've proven that many times," said Norris.
Ferrari pair Charles Leclerc and Lewis Hamilton were fourth and fifth, although seven-time champion Hamilton has a five-place grid penalty and will struggle to bring any joy to what has been a difficult first season with the Scuderia.
Hamilton is yet to obtain even a podium finish in a GP this season, and the 40-year-old sits 200 points behind Piastri having finished ahead of Leclerc just twice all season.
Another home hope, Kimi Antonelli, was seventh fastest but will start in sixth, one place behind his Mercedes teammate George Russell, thanks to Hamilton's penalty.
The Bologna-born teenager, who was announced as a Mercedes driver at Monza last year, gave himself a good chance of turning around a rotten recent run.
Fellow rookie Isaac Hadjar, who failed to get past Q1, is unlikely to repeat last weekend's feat of a podium finish as he is set to start from the pitlane due to a power unit change.
France's Pierre Gasly starts from the ninth row of the grid after failing to get past an extremely tight Q1 in which less than a second separated all 20 cars.
Liam Lawson sits at the rear of the field with his Racing Bulls teammate Hadjar waiting in the wings.