Heat oven to 375°F (190ºC) with rack set in middle position. Line a baking sheet with foil then set a wire rack in sheet.
Arrange bacon in a single layer on rack and bake 20 minutes.
Combine sugar, chili powder, and cayenne pepper in a small bowl; evenly sprinkle on bacon slices then return to oven and bake until crispy, 15–20 minutes more.
Make ahead tip: cook the bacon halfway through (before adding the spice mixture) then store in a zipper-lock bag in the refrigerator. Day of, arrange bacon on rack in sheet pan and reheat for 5 minutes at 375°F (190ºC) before topping with sugar mixture and continuing to bake.If you're using regular bacon, skip the pre-cooking step and top the raw bacon slices with the sugar mixture right off the bat.
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