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Adjust oven rack to middle position and preheat oven to 350°F (175°C). Grease a 9- by 13-inch baking pan with nonstick spray and dust with flour.
Sift flour and cocoa powder into a large bowl. Add sugar, baking powder, baking soda, and salt; whisk to combine.
In another bowl, whisk coffee, mayonnaise, and vanilla extract until well combined. Add dry ingredients and whisk until just combined.
Scrape batter into prepared pan. Bake until a cake tester comes out clean, about 35 to 38 minutes. Allow to cool completely on a wire rack.
For the frosting, beat butter until creamy. Add confectioners' sugar, cocoa powder, milk, and vanilla extract. Mix until smooth and fluffy.
Spread frosting over cooled cake. Slice and serve.