Preheat oven to 350°. Grease and flour a 9” x 13” baking pan. In a large mixing bowl, combine flour, granulated sugar, and baking soda.
In a medium saucepan, combine butter, cocoa powder, espresso powder(if using), and water. Bring mixture to a boil, stirring constantly. Remove from the heat.
With an electric mixer on medium speed, beat chocolate mixture into dry mixture until thoroughly blended.
Add eggs, buttermilk, and vanilla. Beat for 1 minute (batter will be thin). Pour batter into prepared pan.
Bake for 20 to 25 minutes, or until an inserted wooden pick comes out clean.
Cool for 10 minutes on a wire rack. Carefully spread peanut butter over warm cake. Cool completely.
To Make Frosting: Combine 1/2 cup butter or margarine, 1/4 cup cocoa, and buttermilk in a small sauce pan.
Bring to a boil over medium heat, stirring constantly. Pour over confectioners' sugar, stirring until smooth. Stir in vanilla.
Spread chocolate frosting over peanut butter on the cake. Cut into squares.