Heat oven to 350°F. Lightly spray a shallow baking pan with cooking spray.
Stir together 1/4 cup sugar and warm water, stirring until sugar dissolves. Add pecans; let soak 10 minutes. Drain water and discard.
Stir together remaining 2 tablespoons sugar, cocoa, chili powder, and cayenne pepper in medium bowl. Add pecans; toss until all cocoa mixture coats pecans. Spread coated pecans onto prepared pan.
Bake 10-15 minutes or until pecans start to glisten and appear dry. Stir occasionally while baking. Cool completely. Store in a cool, dry place. Great as a snack with beverages, as an appetizer, or sprinkle on salads.