Preheat your oven to 350 degrees Fahrenheit. Grease 3 6-inch cake pans with non-stick spray, line the bottoms with parchment paper rounds, and set them aside.
In a medium bowl, whisk together the flour, cocoa powder, baking powder, baking soda, and salt. Set aside.
In a large mixing bowl, cream together the butter and granulated sugar until fluffy. Add eggs and vanilla, mixing until smooth.
Gradually add the dry ingredients and buttermilk to the butter mixture, alternating between them, and mixing until smooth. Stir in the hot coffee.
Divide the batter evenly among the prepared cake pans and bake for 39-44 minutes, or until a toothpick inserted into the center comes out clean. Let the cakes cool in the pans for 5 minutes, then transfer them to a wire rack to cool completely.