Preheat oven to 350°F (175°C). Grease three 8-inch round cake pans, line with parchment paper, and grease the paper.
Sift both cocoa powders together, then whisk with flour, sugar, baking powder, baking soda, and salt until combined.
In a separate bowl, whisk together buttermilk, oil, eggs, vanilla, and vinegar until smooth and frothy.
Add wet ingredients to dry and beat for 2 minutes until smooth. Slowly pour in hot coffee while mixing on low, then mix 30 seconds more until batter is thin and glossy.
Divide batter evenly among prepared pans and tap gently to release air bubbles. Bake 28-32 minutes until toothpick comes out with moist crumbs.
Cool in pans 15 minutes, then invert onto wire racks, remove parchment, and cool completely (at least 1 hour).
Beat softened butter 3-4 minutes until fluffy. Add sifted cocoa and powdered sugar in three additions, then add cream, vanilla, and salt. Beat 3-4 minutes until light and smooth.
Level cake tops if needed. Place first layer on serving plate, spread 3/4 cup frosting on top, add second layer, repeat frosting, then top with third layer.
Apply thin crumb coat over entire cake and refrigerate 30 minutes to firm up.
Apply final layer of frosting to top and sides, smoothing with offset spatula. For best finish, dip spatula in hot water between passes. Refrigerate 1 hour before slicing.