Start by making the Calabrian chili brown sugar syrup. Add 1 cup water, 1 cup brown sugar, and 1 tablespoon chopped jarred Calabrian chilies to a small pot. Heat on medium-low until all the brown sugar has melted, then let cool.
For the cocktail, add ice to a rocks or mixing glass. Then combine it with 2 ounces of bourbon, 1/2 ounce of the chili syrup, 2 dashes smoked chili bitters, and 1 dash orange bitters.