Adjust an oven rack to the middle position and preheat to 350ºF/176ºC.
Grease three 8" cake pans with cake goop or your preferred brand of pan release.
In a medium-sized bowl, whisk together the melted chocolate, cocoa powder, hot coffee, vanilla, and oil until combined (it will look lumpy).
Then mix in the warm buttermilk until everything is combined. Set it aside for now.
Whisk the flour, baking powder, baking soda, and salt in a medium bowl.
Add the softened butter to bowl of your stand mixer with the paddle attachment attached and beat at medium-high speed until smooth and shiny, about 30 seconds.
While mixing on low, gradually sprinkle in the sugar. Continue mixing until the mixture is fluffy and almost white, about 3-5 minutes.
While mixing on low, add the eggs 1 at a time, mixing in fully before adding the next egg.
Whisk the flour, baking powder, baking soda, and salt in a medium bowl.
While mixing on low, add in ⅓ of the flour mixture, then ⅓ of the chocolate mixture. Repeat two more times.
Stop to scrape the bowl after all the ingredients have been added and mix them for 15 more seconds to make sure everything is combined. Don't over-mix.
Divide the batter evenly between the prepared pans. Smooth the tops with a rubber spatula.
Bake the cakes until they feel firm in the center and a toothpick comes out clean or with just a few crumbs on it, about 30-35 minutes.
Transfer the pans to a wire rack and let them cool for 20 minutes.
Invert the cakes onto the rack and pop the cakes out of the pans. I freeze my layers for about 1 hour before frosting them, which helps lock in the moisture.