Preheat oven to 350°F (175°C). Grease three 8-inch cake pans. Line bottoms with parchment and grease parchment.
Whisk flour, cocoa powder, baking powder, baking soda, and salt in a bowl.
In a second bowl, whisk sugars, eggs, oil, buttermilk, coffee liqueur (or coffee), and vanilla.
Combine wet and dry ingredients. Mix just until no dry streaks remain.
Slowly whisk in hot coffee (or hot water) until smooth.
Divide batter evenly among pans.
Bake 22 to 26 minutes, until a toothpick comes out with a few moist crumbs.
Cool 10 minutes in pans, then turn out onto racks and cool completely.