Combine first 3 ingredients in a small saucepan; bring to a boil. Cover, reduce heat, and simmer 25 minutes. Uncover and simmer 5 minutes. Place peach mixture in a food processor; process until smooth. Add 3/4 teaspoon salt, 1/8 teaspoon black pepper, vinegar, and next 4 ingredients (vinegar through red pepper); pulse to combine. Let stand 5 minutes. Place half of peach mixture in a large heavy-duty zip-top plastic bag; reserve other half for basting. Add chops to bag; seal bag and refrigerate 30 minutes to 4 hours.
Remove pork from bag; discard marinade. Sprinkle pork with 1/4 teaspoon salt and 1/8 teaspoon black pepper. Place pork and peach halves on grill rack coated with cooking spray, and grill 10 minutes or until the pork is done and the peaches are tender, turning once. Baste pork and peach halves with the reserved peach mixture every 2 minutes during the first 6 minutes of cooking.