Rebounding from two weekends where he lost ground in the standings -after winning the first two races of the play-off - the two-time Cup champion beat the benchmark set by fellow title contender Matt Kenseth by 0.006s in order to win his first pole position in more than a year.
"I thought we could pick up time [relative to practice] because we were watching lap times and guys weren't picking up as much [time] as we're used to seeing here at Charlotte," said Stewart. "I knew [Stewart Haas team-mate] Ryan [Newman] would put in a good lap.
"I rely on Ryan a lot when it comes to qualifying because he's the master at it for sure. So just took some of the information he gave us and went forward.
"It'd be nice to be the first guy to get to the start-finish line at the start of the race this week. This is a place where track position is really important so this is an awesome start for our team."
The Roush Fenway Fords of Kenseth and Chase leader Carl Edwards were two of a total four Fusions in the top-five as Richard Petty's AJ Allmendinger and Roush's Greg Biffle were fourth and fifth, ahead of Stewart's team-mate.
Richard Childress Racing's Paul Menard and Red Bull's Kasey Kahne had been fastest earlier in practice but could not improve significantly on their qualifying runs and ended up seventh and eighth ahead of reigning champion Jimmie Johnson.
Most of the title contenders were spread through the field, RCR's Kevin Harvick pipping Hendrick's Dale Earnhardt Jr from provisional pole after his run but ending up just inside the top-15 in the order.
Penske drivers Kurt Busch and Brad Keselowski were among those not enjoying solid qualifying runs – ending up 20th and 26th respectively.
Trevor Bayne was the fastest of those having to make the race on speed, securing a top-ten starting spot on his series' return after last racing a Cup car five weeks ago at Chicagoland Speedway. Former Truck Series champion Geoffrey Bodine, Scott Speed and Josh Wise failed to make the field.
Teams will run two practice sessions on Friday focusing on race preparations ahead of Saturday night's event.
Times to follow.
