The defending Formula One champion secured his 10th pole of the season with a lap of 1 minute, 22.275 seconds on the 3.6-mile track at Monza.
Vettel covered the circuit nearly a half-second faster than McClaren's Lewis Hamilton. Red Bull has won all 13 F1 poles this season.
"On the second run, I had one or two cars ahead of me, which always helps at Monza," Vettel said. "We didn't expect to get the pole by that big of a margin."
Jenson Button of Red Bull took the third position Saturday with a 1:22.777. Fernando Alonso of Ferrari will start in fourth position in Sunday's race.
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