Heat grill to medium. Once it is hot, clean the grill grate with a wire brush.
Brush the pork chops with 1 tablespoon of the olive oil and season with the thyme and ½ teaspoon each salt and pepper. Grill until an instant-read thermometer inserted into the thickest part registers 135° F, 7 to 9 minutes per side. Continue grilling, basting the pork chops with the vinegar, until glazed, 2 to 3 minutes. Let rest for 5 minutes.
Meanwhile, toss the broccolini with the remaining 2 tablespoons of olive oil and ¼ teaspoon each salt and pepper. Grill, turning occasionally, until lightly browned and crisp-tender, 5 to 7 minutes. Grill the bread until grill marks appear, 1 minute per side.
Serve the pork chops with the broccolini, bread, and lemon wedges for squeezing.