Brock Osweiler threw an 11-yard touchdown pass to ranked Missouri Tigers, 37-30.
Missouri kicker Grant Ressel had a chance to win the game in the final seconds of regulation, but his 48-yarder sailed wide left.
Arizona State, sporting its slick new all-black uniforms, got the ball to begin overtime. On the fifth play, Osweiler threw the ball out into the flat for Miles. The junior wide receiver sprinted into the end zone to send the "Black Out" crowd into a frenzy.
Arizona State's defense needed just four plays to stop the Tigers and pull off the upset.
"I cannot thank our fans enough. That is college football. That is a college football atmosphere and they were there until the end," ASU head coach Dennis Erickson said."
Osweiler completed 24-of-32 passes for 353 yards and three touchdowns for the Sun Devils (2-0), who won 48-14 over UC Davis last week. He also carried the ball five times for 34 yards and a score.
Miles had two receiving touchdowns and also threw for a score on a trick play. He ended with six catches for 50 yards. Aaron Pflugrad had a career game, hauling in eight passes for 180 yards and two touchdowns.
James Franklin connected on 26-of-42 passes for 319 yards and two touchdowns for the Tigers (1-1), who narrowly defeated Miami-Ohio, 17-6, at home last week. He also carried the ball 27 times for 84 yards and a score.
Down by two touchdowns, 30-16, early in the fourth quarter, Missouri stormed back to tie the game. The Tigers got things going by recovering a muffed punt by Arizona State. A defensive pass interference call on third down set up the Tigers at the 25. L'Damian Washington caught a pass in the middle of the end zone on the next play to make it a 30-23 game with 12 minutes left.
Missouri took over at its own 42 on its next possession. Franklin used his legs to get a fresh set of downs on 4th-and-1 near midfield. Marcus Lucas caught a 49-yard pass to put the ball at the two. On 4th-and-goal from the three, Franklin found his big tight end, Michael Egnew, in the middle of the end zone to make it 30-30 with 2:50 to play.
The Tigers' defense forced a big three-and-out, and Missouri got the ball back at its own eight with under 1 1/2 minutes to go. On the first play, Henry Josey rushed 39 yards down the left sideline. Franklin got the Tigers to the Arizona State 30-yard line. In an interesting move, Missouri called two timeouts in the final seconds before Ressel missed from 48 yards out.
"I thought that we were not as disciplined as we were last week," Erickson said. "We had more penalties. No real stupid ones but we did have some penalties, pass interference calls and all that but the bottom line is that we put it in there at the end and came out on defense and won the football game. Jamal [Miles] fumbles that punt and we had that 14-point lead, that was really the turning point to getting them back in the football game."
The crowd had upset in mind after Miles caught a 12-yard TD pass midway through the first quarter. Ressel's 24-yarder made it 7-3 after 15 minutes of action.
Alex Garoutte's 47-yard field goal early in the second period made it 10-3. The Tigers quickly responded with a 12-play, 70-yard scoring drive to tie the game. Franklin capped the big drive with a two-yard rushing touchdown.
On the first play of Arizona State's ensuing possession, Pflugrad hauled in a 60-yard TD pass. The extra point was blocked to keep it a 16-10 game.
That was the score at the half because Ressel missed a 54-yard field goal in the final seconds.
Ressel was good from 47 yards out early in the third frame to make it a three- point contest. Ressel added a 19-yarder on Missouri's next possession to tie the game.
The Sun Devils used a trick play to take the lead. Osweiler threw behind the line to the right side for Miles, who caught the ball before throwing a pass. A perfect strike to the end zone landed in the hands of Pflugrad for a 35-yard score.
Arizona State capped the third and fourth frames with a seven-play, 60-yard scoring drive. A defensive pass interference call put the ball at the Missouri 12. Osweiler rumbled up the middle on the next play and found the end zone for a 30-16 lead with 14:23 left in the fourth.
Friday's game was the first between the two programs since 1990. The all-time series is tied, 3-3...The Tigers had won 22 straight non-conference games during the regular season, a streak that dated back to 2005...There were 23 penalties in the game.