Vettel's Red Bull team swept the front row in qualifying, with the 26-year-old German in awesome form and teammate Mark Webber just behind in second.
Seeking his third win at the Autodromo Nazionale, the series leader and defending triple world champion Vettel clocked a best lap time of one minute and 23.755 seconds ahead of Webber, who recorded a best of 1:23.968.
They were the only two drivers to go below 1:24.
German Nico Huelkenberg delivered a stunning late lap to snatch third place for Sauber ahead of the Ferraris of Brazilian Felipe Massa and Spaniard Fernando Alonso, who were a disappointing fourth and fifth in front of watching Ferrari president Luca di Montezemolo.
German Nico Rosberg was sixth for Mercedes while his teammate Hamilton qualified only 12th after running off the circuit during Q2.
Daniel Ricciardo, the young Australian who will succeed compatriot Webber at Red Bull next season, was seventh ahead of the two McLarens of Mexican Sergio Perez and Briton Jenson Button, with Frenchman Jean-Eric Vergne completing the top 10 for Toro Rosso.
On another hot late summer's day in the old royal park, Vettel was in dominant form in Q1, setting the pace ahead of the McLaren pair of Rosberg and Hamilton.
The air temperature was a balmy 30 degrees celsius, but on the track it was 43 degrees. As if any confirmation of the level of competition was needed, it was shown by the fact that the top 15 drivers were separated by just seven-tenths of a second.