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Preheat oven to 350°F. Grease 6 muffin cups or place 6 liners in a muffin pan. Set aside.
With a stand mixer or hand mixer, combine sugar, flour, cocoa powder, baking powder, baking soda, and salt. Add egg, milk, oil, and vanilla extract and beat until well combined, scraping the sides and bottom of the bowl as necessary. Add hot coffee and beat until just combined. Batter will be thin.
Divide evenly between 6 prepared muffin cups. Bake for 15-18 minutes, until the tops spring back when you touch them, and a toothpick inserted into the center comes out clean. Transfer the pan to a wire rack to cool completely.
Beat butter and powdered sugar for several minutes, until smooth. Add vanilla extract and milk, and beat for several more minutes, until light and fluffy. If the frosting seems a little too thick, beat in a splash of milk. If it seems too thin, add another tablespoon of powdered sugar.
Frost the cooled cupcakes using a decorating tip or a butter knife. Garnish with sprinkles or chocolate shavings, if desired.