Preheat your oven to 350°F (175°C) and line your cupcake pan with cupcake liners.
In a large mixing bowl, combine the devil's food cake mix, instant chocolate pudding mix, sour cream, vegetable oil, beaten eggs, vanilla extract, and the dissolved espresso granules. Use an electric mixer on medium speed to mix until the batter is smooth and well combined.
Using a spoon or an ice cream scoop, fill each cupcake liner about halfway with the cake batter.
Take your frozen Reese’s Miniatures and gently press one into the center of each cupcake batter-filled liner.
Spoon a little more batter over each Reese’s Miniature until the liners are about three-quarters full.
Place the cupcake pan in the preheated oven and bake for 18-20 minutes, or until a toothpick inserted into the center comes out clean.
Once baked, remove the cupcakes from the oven and allow them to cool in the pan for 5 minutes. Then, transfer them to a wire rack to cool completely before frosting.
In a clean mixing bowl, beat together the softened unsalted butter and creamy peanut butter until smooth and creamy. Gradually add the sifted confectioners' sugar and vanilla extract, mixing until combined.
Once the cupcakes are completely cool, generously frost each one with the peanut butter frosting using a spatula or a piping bag for a more decorative touch.
These Peanut Butter Cup Cupcakes are now ready to be devoured!