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Pat the chicken thighs dry with paper towels. Rub them all over with the olive oil, then season evenly with the salt, black pepper, smoked paprika, and garlic powder. Let the thighs rest at room temperature for 30 minutes while you prepare the grill and sauce.
Combine the ketchup, apple cider vinegar, brown sugar, tamari, Worcestershire sauce, smoked paprika, onion powder, garlic powder, and cayenne (if using) in a small saucepan over medium heat. Stir until the sugar dissolves, then simmer for 8–10 minutes, stirring occasionally, until the sauce thickens slightly and coats the back of a spoon. Remove from heat and set aside. Reserve about 1/3 cup of the sauce in a separate bowl for serving — do not use this portion for basting.
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