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Preheat oven to 450 degrees. Cut radicchio into quarter wedges. Toss with a drizzle olive oil, thyme, sea salt and pepper.
Arrange wedges on baking sheet. Roast 12 minutes, until wilted. Turn over and roast other side another 8 minutes, until tender.
Arrange radicchio on platter, drizzle with balsamic vinegar, and serve.