Preheat oven to 350°F (175°C). Grease two 8-inch round cake pans, line with parchment paper, and grease again.
In a medium bowl, whisk sifted cocoa powder and boiling water until smooth. Set aside to cool slightly.
In a large bowl, whisk together flour, sugar, baking powder, baking soda, and salt.
In another bowl, whisk buttermilk, oil, eggs, and vanilla until combined.
Add wet ingredients to dry ingredients; stir until just combined. Mix in cocoa mixture until smooth.
Divide batter evenly between prepared pans. Bake 25-30 minutes, until a toothpick inserted in center comes out clean.
Cool cakes in pans for 10 minutes, then turn out onto a wire rack to cool completely.
For filling, beat softened butter in a stand mixer until creamy. Add marshmallow fluff and beat on high until light and fluffy, about 3 minutes.
Place one cooled cake layer on a serving plate. Spread marshmallow filling evenly over top, leaving a small border. Top with second cake layer.
For ganache, place finely chopped chocolate in a heatproof bowl. Heat heavy cream until just simmering, then pour over chocolate. Let sit 2 minutes, then stir until smooth.
Pour ganache over top of cake, letting it drip down sides. Smooth with an offset spatula if needed. Chill at least 1 hour before slicing.