McLaren's Lewis Hamilton, nearly half a second slower than the German in the final session, will line up alongside the championship leader on the front row with team-mate Jenson Button in third place.
Ferrari's Fernando Alonso, last year's winner from pole position at the fastest track on the calendar, qualified in fourth place in his team's home race.
It was Vettel's 10th pole of the season, four shy of Briton Nigel Mansell's 1992 record of 14, and the 25th of his 75-race career.
Red Bull have now been on pole for the past 14 races, with Vettel also quickest at last year's Abu Dhabi season-ender.
"We thought it would be much closer than that," said Vettel, who won from pole at Monza with Red Bull's Italian-based sister team Toro Rosso in 2008, after taking the top slot with a lap of one minute 22.275 seconds.
"This year I have to say the car is so good here. The balance is perfect."
Red Bull Racing have yet to get one of their drivers on the podium at Monza but Vettel, 92 points clear of Australian team-mate Mark Webber with seven races remaining, should end that on Sunday.
"I remember the last time and hopefully I am back on the podium tomorrow," he smiled.
"I didn't have another half a second in the bag," said Hamilton, who lapped in 1:22.725, of the demoralising gap between him and the 24-year-old Vettel.
Webber, who has yet to win this season, lines up fifth alongside Ferrari's Felipe Massa and ahead of Renault's Vitaly Petrov and former Ferrari ace Michael Schumacher, now with Mercedes.
Brazilian Bruno Senna, in his second race with Renault, will again start in the top-10 and next to Mercedes' Nico Rosberg.
Senna pips Di Resta
Paul di Resta was pipped by Renault’s Bruno Senna in the dying minutes of the Q2 session as none of the Force India cars made it to the top-10.
Resta (1:24.163) was in contention for Q3 till the last minute but Senna (1:24.157) pushed him to 11th by just six thousands of a second in his last attempt.Resta’s team-mate Adrian Sutil was 12th with the best lap of 1:24.209.
Both the Force India drivers will start in the sixth row in Sunday’s race.
