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Preheat oven to 450 degrees F. Coat a large baking sheet with cooking spray.
To prepare cabbage: Cut cabbage half into four wedges and cut out any thick core, leaving the wedges as intact as possible. Drizzle the cut sides with 1 tablespoon oil and sprinkle with ¼ teaspoon each salt and pepper. Place the wedges flat-side down on the prepared baking sheet.
Roast the cabbage for 12 minutes. Carefully flip over (it's OK if it falls apart a little) and roast until browned on both sides, about 8 minutes more.
To prepare vinaigrette: Combine mustard, vinegar, lemon juice, pepper and ⅛ teaspoon salt in a small bowl. Add chives and oil; stir until well combined.
Transfer the cabbage to a serving plate (or plates) and drizzle with the vinaigrette while still hot. Serve hot or room temperature.