Prepare the cake pans: Preheat oven to 350°F (175°C). Grease and line two 9-inch round cake pans.
Bloom cocoa: In a heatproof bowl, whisk cocoa powder with boiling water until smooth. Let cool slightly.
Mix dry ingredients: In a large bowl, whisk flour, sugar, baking powder, and salt.
Add wet ingredients: Stir in milk, oil, eggs, and vanilla until smooth. Fold in the cocoa mixture.
Bake cakes: Divide batter evenly into pans and bake for 30–35 minutes, or until a toothpick comes out clean. Cool completely.
Make frosting: Heat cream in a saucepan until steaming. Pour over chopped chocolate, cocoa, espresso powder, vanilla, and salt. Let sit 2 minutes, then stir until smooth. Add butter and confectioners’ sugar, whisking until fluffy. Chill until spreadable.
Assemble cake: Spread frosting between cooled cake layers, then cover top and sides with remaining frosting.
Make marshmallow web: Place marshmallows in a microwave-safe bowl, spray lightly with cooking spray, and heat in 10-second intervals until melted. Use greased hands to stretch strands of marshmallow across the cake for a web or mummy effect.
Decorate: Add candy spiders for a web cake or candy eyes for a mummy cake. Chill before serving.