Washington State took a 33-17 lead on Drew Dunning's 37-yard field goal with 7:37 left in the fourth quarter, his fourth of the game.
But Kyle Orton, who threw 72 passes, hooked up with Taylor Stubblefield on a 50-yard touchdown with 1:53 remaining and Purdue recovered the ensuing onside kick.
Orton drove the Boilermakers to the Washington State 22 with completions of 21 and eight yards to John Standeford. But Orton threw three straight incompletions and the Cougars ran out the clock to seal the win.
Washington State (10-2), which trailed faced a 20-17 deficit at intermission, also reached 10 wins in 1929 and 1997, when Ryan Leaf led Washington State to the Rose Bowl.
The Pac-10 had been 0-3 in the postseason, with Southern California, Stanford and Washington suffering losses. The conference will get another chance for a win when Oregon, which is entertaining hopes of gaining a share of the national championship, faces Colorado in the Fiesta Bowl on Tuesday.
The loss continued Purdue's late-season slide as the Boilermakers (6-6) lost five of their last six games to finish at .500 following a 5-1 start.
Washington State's Jason Gesser completed only six of his first 27 passes, but responded with a number of big completions in the second half.
Gesser's 50-yard completion to Jerome Riley set up his one-yard sneak that snapped a 20-20 tie with 3:04 remaining in the third period. Dunning converted three field goals in the second half.
With a 30-20 lead, Washington State missed a chance to put away the contest when cornerback Antwaun Rogers intercepted Gesser in the end zone.
Orton drove Purdue to the Washington State 20, but the Boilermakers came up empty when Lamont Thompson picked off a pass in the end zone. Thompson, the Pac-10's all-time leader in interceptions, finished his career with 24, including two on Monday.
Dunning kicked a 37-yard field goal to give the Cougars a 13-point led with 7:37 left.
Purdue turned the ball over on downs when Orton's pass was incomplete on fourth and one from the Washington State 25 with just over three minutes left. But the Boilermakers forced the Cougras to punt and Orton went to work on his belated comeback attempt.
Washington State jumped to a 14-0 lead just over eight minutes into the first quarter on Jason Reed's 45-yard interception return and Gesser's 46-yard strike to Mike Rush.
But the Boilermakers erupted for 20 points in the second period. They tied the contest, 17-17, on Orton's three-yard pass to Taylor Stubblefield with 1:56 left in the quarter and took a 20-17 halftime lead on Travis Dorsch's 51-yard field goal with 37 seconds left.

