Preheat the oven to 425 degrees F (220 degrees C). Line a sheet pan with parchment paper or foil.

Trim excess skin and fat from thighs and pat dry with paper towels. Place chicken thighs in a 1-gallon resealable plastic bag.

Stir together salt, pepper, and baking powder in a small bowl until well blended. Add seasonings to the bag. Seal the bag; shake and move chicken around to evenly coat with seasonings.

Place seasoned chicken thighs on the prepared pan, skin side up, and spray with olive oil spray.

Bake in the preheated oven until chicken skin is brown and crispy, chicken is no longer pink at the center and juices run clear, 40 to 45 minutes. An instant-read thermometer inserted near the center of chicken should read at least 165 degrees F (74 degrees C).

Meanwhile, melt butter in a small saucepan over medium heat. Stir in hot sauce, Worcestershire sauce, garlic, and cayenne. Remove from heat and keep warm.

Remove chicken from the oven; brush thighs evenly with hot sauce mixture.