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Preheat oven to 375°F. Lightly coat twenty-four ¼-inch muffin cups with cooking spray.
In a medium bowl, stir together flour, sugar, baking powder, baking soda, salt, and cayenne pepper. Stir in Parmesan cheese and chives. Make a well in the center of the flour mixture.
Whisk together eggs, buttermilk, and melted butter in another medium bowl. Add egg mixture all at once to flour mixture. Stir just until moistened (batter should be lumpy). Spoon batter into prepared muffin cups, filling each nearly full.
Bake 10 to 12 minutes or until golden. Cool in pan on a wire rack 5 minutes. Remove from pan. Serve warm.