Sauber's Sergio Perez was eighth, ahead of the Williams of Pastor Maldonado and Nico Rosberg's Mercedes.
Michael Schumacher was 14th in his fourth last F1 qualifying session - he was behind Lotus's Romain Grosjean, Force India's Nico Hulkenberg and Williams driver Bruno Senna and was 0.6secs slower than team-mate Rosberg.
"I made a mistake on my first run so we only had one set of tyres left but I was pretty happy with the [final] lap," said Vettel. "It has been a great weekend so far, no problems with the car. We need to keep pushing; we have a lot of important races to go but the best chance of doing well is to focus on every single step.
He added: "You know that a lot of things can happen in the race. I am very happy to be on pole but there is a hard race coming tomorrow. We had a bit of a surprise on Friday on the long runs, everyone was quite close, so we'll see what that means with strategy tomorrow."
The margins at the front were not as great as expected, with Webber closer to Vettel than he had been for most of the weekend and the McLarens likewise closer to the Red Bulls.
"The lap itself wasn't too bad," said Webber. "I got onto the Astroturf at the last corner so it wasn't the smoothest run to the finish line, but I'm driving the car.
Vettel's pole lap in India
"Then I didn't get to do my final lap, the McLarens were doing very slow out-laps so I didn't get my second lap. I had no front grip at the start of my lap so it was finished. So I was surprised to end up second - I'll take that."
Alonso appeared to have the potential to sneak onto the second row, but a wheel locked on his entry to Turn Four on his final qualifying lap and he failed to improve on the time he set on his first run earlier in the top 10 shoot-out.
But he said that he was already down on his best time before that incident, and that he had been struggling to get the best out of the tyres on their first lap. He added that he did not think he would have been able to out-qualify the McLarens.
Third-placed Hamilton said: "We're not quick enough to be ahead of these guys but we can definitely challenge them in the race. Our race pace was just as good as theirs in practice so I'm excited about that."
It was the third consecutive front-row lock-out for Red Bull, who are in imperious form following a series of car upgrades that started at
the Singapore Grand Prix
four races ago.
Indian Grand Prix 2012, day two
Saturday, 27 October: Qualifying highlights: 13:00-14:15 BST, BBC One
Indian Grand Prix 2012, day three
Sunday, 28 October: Race: 09:30 GMT 5 Live & online; Race highlights: 14:05-15:45 GMT, BBC One; repeated BBC Two 01:00-02:40 GMT
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