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In the 3rd town when you go to the Tower of mastery, your friend gives you an item. In the same town, you can trade that item with a Hiker for a Sun Stone.

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Intriguing stone. Also, it's not in the third town, its in Shalour city, which is the 3rd CITY. -Gel Low Ham Stir
Actually, it's the 4th city. 1 Santalune City, 2 Lumiose City, 3 Cyllage City, and 4 Shalour City