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Preheat oven to 350°F. Combine flour, 1/4 cup sugar and baking powder in a medium bowl. Add milk, oil and vanilla. Using a wire whisk, stir until smooth. Stir in peanut butter and semisweet chocolate pieces.
Pour batter into an ungreased 1-quart casserole dish; set aside. In the same bowl, stir together the remaining 1/2 cup sugar and cocoa. Gradually stir in boiling water. Pour mixture over batter in casserole.
Bake, uncovered, for 35 to 40 minutes or until a wooden toothpick inserted into cake portion comes out clean. Remove from oven; top with peanuts and, if desired, graham crackers. Serve warm with whipped cream, if desired.