Preheat your oven to 350°F (175°C). Line two 8-inch round cake pans with parchment paper and grease them lightly with baking spray for easy release.
In a medium-sized bowl, whisk the Dutch-processed cocoa powder with hot brewed coffee until fully dissolved and smooth, ensuring no lumps remain. Incorporate the warm melted chocolate and whisk until well-blended. Set this mixture aside to cool slightly.
In another bowl, combine the all-purpose flour, baking powder, baking soda, and salt. Whisk until these dry ingredients are thoroughly mixed.
In a large bowl, whisk together the eggs, white sugar, sour cream, vegetable oil, and vanilla extract until smooth and creamy. Slowly pour in the cocoa-coffee-chocolate mixture and whisk until everything is silky and well-combined.
Gradually add the dry ingredients to the wet mixture, stirring until the batter is smooth and fully incorporated.
Divide the cake batter evenly between the prepared cake pans. Bake for 40-45 minutes, or until a toothpick inserted into the center of each cake comes out clean. If the cakes are not done, bake for an additional 5 minutes and test again.
Let the cakes cool in their pans for about 30 minutes. Once cooled, gently remove them from the pans and transfer to a wire rack to finish cooling completely.