1. Roast peppers directly over the flame of a gas-stove burner or under a broiler, turning often, until charred on all sides, about 5 minutes. Transfer to a plastic bag, and let stand 15 minutes. Peel peppers, and discard stems, seeds, and ribs. Tear flesh into thick strips.

2. Heat a large cast-iron skillet over high heat. Generously season chops on both sides with salt and pepper. Brown chops on both sides, turning once, about 4 minutes total.

3. Stir in garlic and capers, and cook 30 seconds, stirring to prevent garlic from burning. Add wine, and cook, stirring and scraping up browned bits as wine reduces to a glaze, about 3 minutes. Add roasted peppers.

4. With pan still very hot, add vinegar, and cook 2 minutes, swirling skillet as vinegar bubbles. Reduce heat to medium. Cover, and cook until chops are cooked through and internal temperature reaches 138 degrees (they should be slightly pink inside), 4 to 5 minutes. Serve pork chops and peppers over polenta.