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Preheat the oven to 325°F and line two 12-cup muffin tins with paper liners.
In a large bowl, whisk together the sugar, flour, cocoa powder, baking powder, baking soda, and salt. Set aside.
In a separate medium bowl, whisk together the eggs, milk, oil, and vanilla.
Pour the egg mixture into the dry ingredients, mixing until just incorporated. Scrape down the bowl with a rubber spatula.
In a liquid measuring cup, dissolve the instant espresso powder in the boiling water. Carefully whisk this mixture into the cake batter until fully combined. Scrape the bowl again.
Use a #20 scoop or a ¼-cup dry measuring cup to evenly scoop the batter into the prepared muffin cups.
Place the muffin tins in the preheated oven and bake for 22 to 25 minutes, or until a cake tester inserted into the center comes out clean.