Heat a charcoal or gas grill to medium temperature (about 350°F). Halve and pit the peaches.
When the grill is heated, place peaches cut side down on the grate and grill until they have grill marks and are slightly softened, about 5 minutes. Rotate peaches 90 degrees and continue grilling until the skin shrivels a bit and the flesh becomes tender, about 3 minutes more. Remove from the grill.
To assemble the sundaes, place one grilled peach half in each serving dish and top with a large scoop of ice cream. Crumble one piece of Baklava over the top and, if desired, drizzle with 1 tablespoon of the ouzo. Serve immediately.
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