The Michael Waltrip Racing driver set a fastest lap of 22.641 seconds at an average speed of 159.004 mph, beating Penske's Busch by just three thousandths of a second to claim his first pole position of the season at the track where he got his only Cup victory thus far, back in 2007.
"We've had a really good car the last couple of times we've been here," said Truex. "The team did an awesome job tuning it up for qualifying. Hopefully tomorrow we'll put it all together but it was just a great lap."
He added: "We worked through a lot of things yesterday in practice and felt like the car was good. Then we went to the second practice and fought some things. But I think we found a little bit of an issue in the car and we'll have it dialled in."
Chase contenders ended up spread through the 43-car field, although four of the 12 title hopefuls claimed top-six starting spots.
Richard Childress Racing's Paul Menard, who had been fastest in the opening practice on Friday and among the most consistent in the second one, set the third fastest time of the session after running last in the order.
Behind Menard, Roush Fenway's Carl Edwards was fourth, Joe Gibbs Racing's Kyle Busch fifth while six-time Dover winner Jimmie Johnson was sixth fastest, his best result in qualifying during the Chase so far.
Richard Petty's AJ Allmendinger was seventh ahead of JTG Daugherty's Bobby Labonte, who held provisional pole for a good portion of the session. Red Bull's Kasey Kahne and Roush's Greg Biffle - a two-time Dover winner - rounded out the top 10.
Chase leader Tony Stewart, who struggled during Friday's practice, had yet another lacklustre qualifying effort - finishing 28th, which will be his worst starting position since the play-off started.
Even further back than the two-time champion was Hendrick Motorsports' Jeff Gordon, who was 34th fastest, his worst in qualifying during the whole season.
Josh Wise was the fastest of the non-guaranteed drivers in 26th, while Mike Skinner was the only driver who failed to qualify after slapping the wall during his run.
Pos Driver Team/Car Time Gap 1. Martin Truex Jr Waltrip Toyota 22.641s 2. Kurt Busch Penske Dodge 22.644s + 0.003s 3. Paul Menard Childress Chevrolet 22.689s + 0.048s 4. Carl Edwards Roush Fenway Ford 22.705s + 0.064s 5. Kyle Busch Gibbs Toyota 22.706s + 0.065s 6. Jimmie Johnson Hendrick Chevrolet 22.712s + 0.071s 7. AJ Allmendinger Petty Ford 22.723s + 0.082s 8. Bobby Labonte JTG Daugherty Toyota 22.738s + 0.097s 9. Kasey Kahne Red Bull Toyota 22.744s + 0.103s 10. Greg Biffle Roush Fenway Ford 22.761s + 0.120s 11. Denny Hamlin Gibbs Toyota 22.801s + 0.160s 12. Marcos Ambrose Petty Ford 22.826s + 0.185s 13. Jeff Burton Childress Chevrolet 22.829s + 0.188s 14. David Reutimann Waltrip Toyota 22.831s + 0.190s 15. Brad Keselowski Penske Dodge 22.832s + 0.191s 16. Regan Smith Furniture Row Chevrolet 22.832s + 0.191s 17. Mark Martin Hendrick Chevrolet 22.849s + 0.208s 18. Matt Kenseth Roush Fenway Ford 22.857s + 0.216s 19. David Ragan Roush Fenway Ford 22.866s + 0.225s 20. Ryan Newman Stewart Haas Chevrolet 22.878s + 0.237s 21. Dale Earnhardt Jr Hendrick Chevrolet 22.901s + 0.260s 22. Kevin Harvick Childress Chevrolet 22.905s + 0.264s 23. Jamie McMurray Earnhardt Ganassi Chevrolet 22.924s + 0.283s 24. Juan Pablo Montoya Earnhardt Ganassi Chevrolet 22.935s + 0.294s 25. Landon Cassill Phoenix Chevrolet 22.956s + 0.315s 26. Josh Wise Max Q Ford 22.960s + 0.319s 27. Clint Bowyer Childress Chevrolet 22.964s + 0.323s 28. Tony Stewart Stewart Haas Chevrolet 22.965s + 0.324s 29. Scott Speed Whitney Ford 23.005s + 0.364s 30. Brian Vickers Red Bull Toyota 23.013s + 0.372s 31. David Stremme Inception Chevrolet 23.040s + 0.399s 32. Travis Kvapil Front Row Ford 23.043s + 0.402s 33. Joey Logano Gibbs Toyota 23.068s + 0.427s 34. Jeff Gordon Hendrick Chevrolet 23.082s + 0.441s 35. Michael McDowell HP Toyota 23.097s + 0.456s 36. David Gilliland Front Row Ford 23.120s + 0.479s 37. Andy Lally TRG Ford 23.132s + 0.491s 38. Reed Sorenson Gordon Dodge 23.136s + 0.495s 39. Casey Mears Germain Toyota 23.158s + 0.517s 40. Mike Bliss FAS Lane Ford 23.170s + 0.529s 41. Dave Blaney Baldwin Chevrolet 23.227s + 0.586s 42. Joe Nemechek NEMCO Toyota 23.263s + 0.622s 43. JJ Yeley Front Row Ford 23.273s + 0.632s 44. Mike Skinner Germain Toyota 23.404s + 0.763s