Vettel, a three-time winner in Singapore, always as a driver for Red Bull, posted a fastest lap time of 1:43.885 in Saturday's Q3 and will be joined on the front row by Australian Red Bull driver Daniel Ricciardo.
Finnish Ferrari driver Kimi Raikkonen and Russian Red Bull driver Daniil Kvyat will start third and fourth, respectively, on Sunday at the Marina Bay Street Circuit.
British Mercedes driver Lewis Hamilton has dominated the qualifying sessions during the 2015 F1 season, having snagged pole position for 11 of the 13 races. He also leads the 2015 drivers' standings with 252 points, 53 more than teammate Nico Rosberg.
But on Saturday, Hamilton lagged more than 1.4 seconds behind Vettel in Q3 and will start in the fifth spot on the grid.
Prior to Saturday, a Ferrari driver had not claimed pole position for an F1 race since Spain's Fernando Alonso in the 2012 season.