Pre-heat oven to 350° with rack in the center of the oven. This cake works best in a 10 to 12-inch cast iron pan. Or, use a 10-inch cake pan with high sides.
Melt 3 TBSP butter in cast iron pan. Add brown sugar and a pinch of salt and cook on low until well melted, 2 to 3 minutes, while whisking. Remove from heat.
Carefully, using the prettiest peach slices, place the nicest side face down in pan going in the same direction to form a tight wheel around the edge of the pan. Then fill in the center following the same pattern. Add any leftover peaches to fill in the holes or gaps. The bottom of the pan should be completely covered.
In a large bowl, whisk together All-Purpose Flour, Cornbread Mix, baking powder and soda, and ½ tsp. salt. In a smaller container, whisk together milk, the rest of the melted butter, orange zest, juice, eggs, and ¾ c. sugar until smooth. Stir milk mixture into flour mixture until just combined.
Pour batter over peaches and spread into an even layer, being careful not disturb peaches in the bottom. Bake cake until golden brown and a tooth pick inserted into the center comes out clean, 30 to 35 minutes, rotating skillet half way through for even baking.
Cool on a rack for 15 minutes. Run a knife around edge of the cake and loosen. Place a large flat serving platter over cast iron pan. Using pot holders and being careful not to burn yourself, hold the platter on tight and flip the pan and platter over carefully. Remove pan and replace any peaches that stuck to the pan. Let cool completely, about 1 hour, and serve.
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