Preheat oven to 350°F (175°C) and line a 12-cup muffin pan with cupcake liners.
Whisk flour, black cocoa, Dutch-process cocoa, baking soda, baking powder, and salt together.
In a separate large bowl, combine granulated and brown sugar.
Whisk in eggs and vegetable oil until smooth.
Add sour cream and vanilla and whisk until combined.
Add the dry ingredients and gently mix until mostly incorporated.
Slowly whisk in hot coffee until a smooth, relatively thin chocolate batter forms.
Divide batter among 12 cupcake liners, filling each approximately ⅔ full.
Bake for 17–20 minutes, or until a toothpick comes out clean or with a few moist crumbs.
Cool in the pan for 5 minutes.
Transfer to a wire rack and cool completely.
For the frosting, beat softened butter until creamy.
Gradually beat in powdered sugar and black cocoa.
Add vanilla, salt, and enough heavy cream to create a smooth spreadable consistency.
Add a tiny amount of black gel food coloring if a darker shade is desired.
Spread a smooth, relatively flat layer of frosting over each completely cooled cupcake.
Gently melt the white chocolate and transfer it to a small piping bag.
Pipe 3–4 concentric white chocolate circles over one cupcake.
Immediately drag a clean toothpick from the center outward through the circles approximately 6–8 times to create a spiderweb.
Repeat with the remaining cupcakes, working one at a time.
Add optional edible chocolate spiders.
Allow the decoration to set before serving.