Stir together first 5 ingredients in a large bowl or large zip-top plastic bag; add potatoes. Drizzle with 2 Tbsp. balsamic vinegar, and stir or shake well to coat. Arrange potatoes in an aluminum foil-lined jelly-roll pan coated with cooking spray.
Bake, uncovered, at 450° for 45 minutes or until potatoes are tender, stirring once. Drizzle with remaining 1 Tbsp. vinegar, and toss well. Serve immediately.
*1/4 tsp. dried thyme may be substituted for fresh thyme.