The German Red Bull star, 21, left it until the final hot lap of the closing 10-minute Q3 to demote championship leader Button down to second, with Brawn GP team-mate Rubens Barrichello third.
Button, who has a 16-point lead over Barrichello and 28 to Vettel, said: "We're on the front row, which is a great place to be, but well done to Sebastian for beating us."
As for Lewis Hamilton, it was yet another day of frustration, and this time there was no mistake as in Monaco a fortnight ago when he slid into a barrier in the opening 20-minute session.
On this occasion it was yet another case of the car not being good enough, blowing away the early optimism after yesterday's practice sessions and leaving the champion down in lowly 16th.
Leading Grid Positions after Qualifying: 1 Sebastian Vettel (Ger) Red Bull 1min 28.316secs, 2 Jenson Button (Gbr) Brawn GP 1:28.421, 3 Rubens Barrichello (Bra) Brawn GP 1:28.579, 4 Mark Webber (Aus) Red Bull 1:28.613, 5 Jarno Trulli (Ita) Toyota 1:28.666, 6 Kimi Raikkonen (Fin) Ferrari 1:28.815, 7 Felipe Massa (Bra) Ferrari 1:28.858, 8 Fernando Alonso (Spa) Renault 1:29.075, 9 Nico Rosberg (Ger) Williams 1:29.191, 10 Robert Kubica (Pol) BMW Sauber 1:29.357, 11 Nick Heidfeld (Ger) BMW Sauber 1:27.521, 12 Kazuki Nakajima (Jpn) Williams 1:27.629, 13 Timo Glock (Ger) Toyota 1:27.795, 14 Heikki Kovalainen (Fin) McLaren 1:28.207, 15 Adrian Sutil (Ger) Force India 1:28.391, 16 Lewis Hamilton (Gbr) McLaren 1:28.318, 17 Nelson Piquet Jr (Bra) Renault 1:28.582, 18 Sebastien Buemi (Swi) Scuderia Toro Rosso 1:28.708, 19 Giancarlo Fisichella (Ita) Force India 1:28.717, 20 Sebastien Bourdais (Fra) Scuderia Toro Rosso 1:28.91
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