Make the Cake Layers: Preheat oven to 350°F. Grease and flour three 8-inch round cake pans. In a medium bowl, whisk together the flour, baking powder and salt. In a large bowl, beat the butter and sugar until light and fluffy.
Beat in the eggs one at a time, then stir in the vanilla. Alternate mixing in the flour mixture and milk in three additions. Divide batter evenly between prepared pans. Bake 20-25 minutes until a toothpick comes out clean. Allow cakes to cool completely.
Make the Espresso Syrup: In a small bowl, stir together the hot water, espresso powder, sugar and coffee liqueur until dissolved. Set aside.
Make the Mascarpone Filling: In a large bowl, beat the mascarpone and powdered sugar until smooth. In a separate bowl, beat the heavy cream and vanilla until stiff peaks form. Gently fold the whipped cream into the mascarpone mixture.
Assemble the Cake: Place one cake layer on a serving plate. Brush with 1/3 of the espresso syrup. Spread with 1/2 of the mascarpone filling.
Top with another cake layer, more espresso syrup and remaining filling. Top with final cake layer and frost the top and sides with the mascarpone frosting.
Refrigerate: Refrigerate the cake for at least 4 hours or overnight before serving. Dust with cocoa powder before slicing.
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