It was fifth pole position of the season for Vettel, whose three consecutive wins have propelled him to the top of the table in the drivers' standings.
Vettel's flying lap of 1:25.283 in Q3 secured him the pole, his 35th in the career and he will be joined on the front row by team-mate Mark Webber, who was just 0.34s behind.
It's extremely good result for Vettel since his closest rival in the drivers' classification Fernando Alonso, who is just six points behind at 209, will start the race from fifth position behind the two McLaren cars.
Lewis Hamilton (1:25.544) was third, followed by Jenson Button (1:25.659). Alonso's fastest lap came in 1:25.773, which was good enough only for the fifth position.
His team-mate Felipe Massa, who was excellent in the last two races, can continue his resurgence from the sixth position. Kimi Raikkonen took his Lotus car in the seventh position ahead of Sergio Perez of Sauber.
Williams' Pastor Maldonado and Mercdes' Nico Rosberg, who did not set time in Q3, fill in the fifth row.
"I am happy to be on pole. It's best position to start from. There is a hard race tomorrow as everyone was competitive and tyres lasted quite well. It was special to win the first race in India and to win it for the second time is the target for tomorrow," Vettel said.
"The car was fantastic. It was good that we could work everything well today. We need to concentrate a lot. I pushed as hard as I could. It worked. Fortunately I got the lap together. I could have been faster. But it has been a great week-end so far. The boys have done a great job. We have to keep pushing," the German added.
"It is best to have Fernando behind me than ahead. But you never know. Tomorrow will be a long race. My car is very good in the long run. Let's see how it works," Vettel said.
Sahara Force India's Nico Hulkenberg will start 12th on the grid behind Lotus' Romain Grosjean, who missed the top-10 shootout only for the second time in the season.
Paul di Resta was way behind in 16th position, which is his worst qualifying result of the calendar so far. Bruno Senna of Williams was 13th followed by Michael Schumacher in the second Mercedes and behind him was Toro Rosso's Daniel Ricciardo.
Japanese Kamyui Kobayashi was 17th, followed by Jean Eric Vergne and Vitaly Petrov. India's Narain Karthikeyan, who had finished 17th last year, qualified in the 23rd position behind Hispania temmate Pedro De la Rosa.
Caterham's Heikki Kovalienen, who was 20th, had crashed in the last lap of the Q1 after slipping to the gravel on turn 11. His car, which was stuck, had to be lifted from the gravel to the pits. Charles Pic will be the last man on the grid while his teammate Timo Glock was 21st.