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Adjust the oven rack to the middle position and preheat the oven to 450°F. Place the butter into a 9-by-9-inch casserole dish and set inside the oven while it is preheating.
Place the flour, salt, baking powder, and sugar in a large bowl and whisk to combine. Add the buttermilk and stir gently with a spatula just until combined. Do not overmix.
Remove the hot cast-iron skillet from the oven and gently pour the batter over the melted butter. Use a knife or spatula to spread the dough evenly in the skillet.
Run a knife through the dough, 'cutting' it into 3-inch squares right in the skillet.
Bake for 20 to 25 minutes, rotating the pan once halfway through, until the tops of the biscuits are golden brown. Serve immediately.