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Slice the onion crosswise into ½-inch-thick rounds. Separate the pieces into rings and place in a 9-by-13-inch baking dish. Pour buttermilk evenly over the onions and toss gently to coat. Cover and chill for at least 1 hour or up to overnight.
In a large bowl, whisk together the flour, salt, baking powder, black pepper, and cayenne pepper. Set aside.
In a large Dutch oven, heat 2 inches of oil over medium to 375°F. Working in batches, remove onion rings from the buttermilk, allowing the excess to drip off. Add to the flour mixture and toss well to coat, shaking off the excess. Fry the onion rings, stirring occasionally, until golden brown and crisp, 2 to 3 minutes. Using a slotted spoon, transfer the onion rings to a paper towel-lined baking sheet. Sprinkle the onion rings with additional salt to taste. Serve hot with ranch dressing, if you like.