Combine salt, pepper, onion & garlic powder, cayenne & oregano in a small bowl.
Combine flour and cornstarch in medium bowl. Whisk buttermilk and baking soda in large bowl.
Toss potato wedges with 4 tsp spice mixture and ¼ cup oil in large microwave-safe bowl and cover tightly with plastic wrap. Microwave on high until potatoes are tender but not falling apart, 7 to 9 minutes, shaking bowl (without removing plastic) to redistribute potatoes halfway through cooking. Slowly remove plastic wrap from bowl (be careful of steam) and drain potatoes. Arrange potatoes on rimmed baking sheet and cool until potatoes firm up, about 10 minutes. (Potatoes can be held at room temperature for up to 2 hours.)
Heat remaining 3 quarts oil in large Dutch oven over high heat to 340°F. Meanwhile, dredge potato wedges in flour mixture, shaking off excess. Dip in buttermilk mixture, allowing excess to drip back into bowl, then coat again in flour mixture. Shake off excess and place on wire rack. (Potatoes can be coated up to 30 minutes in advance.)
When oil is ready, fry in batches until deep golden brown, 4 to 6 minutes. Drain on paper towels. Transfer wedges to large bowl and toss with 2 tsp spice mixture. Serve with extra seasoning on side.