Preheat a broiler.
Broil the peppers until the skin has blistered and peppers are cooked through, 7 to 9 minutes. Place in a paper or plastic bag and seal immediately. Let stand for 15 minutes, or until cool enough to handle, this will make them easier to peel. Peel peppers, discard skins.
Place the peeled peppers in a sterilized, heatproof jar with a sterilized, tight fitting lid. In a medium, non-reactive saucepan, bring the vinegar, sugar, water, and pickling spices to a boil. Pour hot mixture over peppers. Place lid on jar and let stand at room temperature for 2 days.