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Bring a small saucepan of water to a boil over high heat. Add garlic and cook for 3 minutes; drain. Transfer the garlic to a 2-cup glass canning jar (or other heatproof jar) with a tight-fitting lid.
Combine 2/3 cup water, vinegar, sugar, salt, peppercorns, mustard seeds, fennel seeds and crushed red pepper in a small saucepan. Bring to a boil over high heat, stirring until the sugar and salt are dissolved. Pour the hot pickling solution into the jar. Let cool to room temperature. Cover and refrigerate for at least 8 hours for the flavors to develop.