Preheat oven and baking sheet to 450°F.
Combine pepper and sugar in small bowl. Quarter cabbage through core and cut each quarter in to 1-inch wedges but try to leave core intact – this will prevent your cabbage wedges from falling apart. You’ll have about 16 wedges.
Brush wedges with oil and sprinkle with sugar and pepper.
Place the seasoned wedges on hot baking sheet and roast until cabbage is tender and lightly browned around edges, about 25 minutes.
Drizzle cabbage with balsamic vinegar.