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Blaney's lap of 26.250 seconds was 0.032 seconds faster than teammate Joey Logano in qualifying on Oct. 17 to claim the top spot.
Points leader Kyle Larson will start outside the top 20 in 22nd after sliding through the first turn on his qualifying lap.
Here's the full starting lineup for Sunday's NASCAR race at Phoenix.
Ryan Blaney, No. 12 Team Penske Ford
Joey Logano, No. 22 Team Penske Ford
Chase Briscoe, No. 19 Joe Gibbs Racing Toyota
Denny Hamlin, No. 11 Joe Gibbs Racing Toyota
Christopher Bell, No. 20 Joe Gibbs Racing Toyota
Tyler Reddick, No. 45 23XI Racing Toyota
Ty Gibbs, No. 54 Joe Gibbs Racing Toyota
Michael McDowell, No. 71 Spire Motorsports Chevrolet
Josh Berry, No. 21 Wood Brothers Racing Ford
William Byron, No. 24 Hendrick Motorsports Chevrolet
Ross Chastain, No. 1 Trackhouse Racing Chevrolet
Connor Zilisch, No. 88 Trackhouse Racing Chevrolet
Todd Gilliland, No. 34 Front Row Motorsports Ford
Daniel Suarez, No. 7 Spire Motorsports Chevrolet
Austin Cindric, No. 2 Team Penske Ford
Chase Elliott, No. 9 Hendrick Motorsports Chevrolet
Chris Buescher, No. 17 RFK Racing Ford
Brad Keselowski, No. 6 RFK Racing Ford
Riley Herbst, No. 35 23XI Racing Toyota
Zane Smith, No. 38 Front Row Motorsports Ford
AJ Allmendinger, No. 16 Kaulig Racing Chevrolet
Kyle Larson, No. 5 Hendrick Motorsports Chevrolet
Bubba Wallace, No. 23 23XI Racing Toyota
Austin Dillon, No. 3 Richard Childress Racing Chevrolet
Shane van Gisbergen, No. 97 Trackhouse Racing Chevrolet
Ryan Preece, No. 60 RFK Racing Ford
Cole Custer, No. 41 Haas Factory Team Chevrolet
Carson Hocevar, No. 77 Spire Motorsports Chevrolet
Erik Jones, No. 43 Legacy Motor Club Toyota
Noah Gragson, No. 4 Front Row Motorsports Ford
Ricky Stenhouse Jr., No. 47 HYAK Motorsports Chevrolet
John Hunter Nemechek, No. 42 Legacy Motor Club Toyota
Ty Dillon, No. 10 Kaulig Racing Chevrolet
Alex Bowman, No. 48 Hendrick Motorsports Chevrolet
Austin Hill, No. 33 Richard Childress Racing Chevrolet
Corey Heim, No. 67 23XI Racing Toyota
Cody Ware, No. 51 Rick Ware Racing Chevrolet
The Freeway Insurance 500 will be broadcast nationally on USA Network. Other streaming options for the race include HBO MAX for in-car cameras for each driver.