Line a large baking sheet with parchment paper; coat paper with cooking spray.
Combine sugar, corn syrup, and butter in a large, heavy saucepan over medium heat. Cook 18 minutes or until a candy thermometer registers 275°, stirring frequently. Add peanuts; cook 3 minutes or until a candy thermometer registers 295°, stirring constantly. Remove from heat; stir in baking soda and chile powder. (The baking soda will cause the mixture to bubble and become opaque.)
Quickly pour mixture onto prepared pan; cover with a sheet of parchment paper. Using a rolling pin, quickly roll mixture to an even thickness. Discard top parchment sheet. Cool mixture completely; break into pieces. Store in an airtight container.