The German recorded his fourth pole of 2010 season with a time of 1:37:587 to equal as Red Bull returned to their season dominance of qualifying.
McLarenÃ¢â‚¬â„¢s Lewis Hamilton overcame a difficult final practice session to take third, with team mate Jenson Button back in seventh.
FerrariÃ¢â‚¬â„¢s Fernando Alonso and Felipe Massa came home fourth and fifth ahead of RenaultÃ¢â‚¬â„¢s Robert Kubica who had shown pace in final practice.
Williams continued their good form this weekend as both Nico HÃƒÂ¼lkenberg and Rubens Barrichello both set a 1:38:428 to take eighth and ninth, with HÃƒÂ¼lkenberg ahead as he set the time first; under pressure Renault driver Vitaly Petrov rounded out the top 10.
VettelÃ¢â‚¬â„¢s time smashed the previous quickest pole time set by Massa in 2008 by just over 1.9 seconds, and was 1.4 seconds quicker than HamiltonÃ¢â‚¬â„¢s pole time last year.
Despite a good outing in final practice Force India will be disappointed with their qualifying with Adrian Sutil finishing thirteenth and Vitantonio Liuzzi fourteenth, despite both cars finishing inside the top 10 in final practice.
Michael SchumacherÃ¢â‚¬â„¢s dismal return to F1 continued as he endured his worst qualifying session to start fifteenth for the race, just three tenths quicker than the Sauber of Pedro De La Rosa, with team mate Nico Rosberg half a second quicker in twelfth.
Toro Rosso’s SÃƒÂ©bastien Buemi continued to show his worth, and promise as a future world champion, as he qualified eleventh and almost a second quicker than team mate Jaime Algerusauri in seventeenth.
Of the newest teams Lotus, celebrating their 500th race, continued to show they are the best-placed to eventually succeed. Jarno Trulli led teammate Heikki Kovalainen to take nineteenth and twentieth, 1.3 seconds slower than SauberÃ¢â‚¬â„¢s Kamui Kobayashi but 1.4 seconds ahead of the leading Virgin Racing car of Lucas di Grassi, and almost 2 seconds quicker than the leading Hispania car of Karun Chandhok.
That is now eight poles from nine races for Red Bull and the grid for tomorrow is set up for a fantastic showdown between Red Bull, McLaren and Ferrari ahead of EnglandÃ¢â‚¬â„¢s World Cup clash with Germany.
Overtaking has been limited on the Valencia Street Circuit in recent years, so expect a bit of a scramble down to the tricky turn two as drivers jostle to get ahead.
The race is live on BBC 2 and the BBC website in the UK from 13:00 BST, with BBCÃ¢â‚¬â„¢s race coverage beginning at 12:10.
MORE: The latest football news
MORE: The latest tennis news
BIOGRAPHY: Daniel Sturridge
BIOGRAPHY: Kepa Arrizabalaga