Preheat oven to 350 degrees F.
Spray a cake pan well with baking spray. In a large bowl, combine butter and sugars. Cream with an electric mixer until smooth and creamy.
Add eggs one at a time, ensuring that each egg is fully incorporated before adding the next.
Add cocoa powder and combine.
Combine the buttermilk, coffee and vanilla in a bowl.
Add cake flour and buttermilk mixture, alternating, 1∕3 at a time.
Beat until just combined. Pour batter into prepared pan.
Bake in oven for approximately 55 - 65 minutes, until a toothpick inserted into the center of the cake comes out clean.
Let cake rest for 10 minutes before removing from the pan.
Allow the cake to cool before pouring on the chocolate ganache.