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Preheat oven to 350 degrees and line a 12-cup cupcake pan with cupcake liners.
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In a bowl, combine cocoa and hot coffee together, whisking until smooth. Set aside.
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With a standing mixer or hand mixer, beat butter until creamy and fluffy, about 2-3 minutes.
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Next, gradually add in granulated sugar and brown sugar, beating 2-3 minutes until it is light and fluffy.
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Add eggs, one at a time, beating just until the yellow disappears.
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Add in the chocolate/coffee mixture, and beat until just combined.
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In a separate bowl, sift together flour, baking soda, baking powder, salt, and espresso powder. Set aside.
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Next, stir together buttermilk, vanilla extract, and sour cream.
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Alternately add the buttermilk mixture and flour mixture to the butter batter, beginning and ending with the flour mixture. Do not overmix.
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Divide batter evenly between muffin cups (the batter makes 14-16).
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Bake for 17-18 minutes, or until a cake tester comes out clean. Be careful not to over-bake, as chocolate cupcakes can get very dry if over-baked.
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Allow to cool.