Place paper baking cup in each of 20 regular-sized muffin cups. Spray insides of paper baking cups with cooking spray. In a large bowl, beat cake mix, water, oil, and eggs with electric mixer on low speed until moistened, then on medium speed 2 minutes, scraping bowl occasionally.
Spoon batter evenly into 20 muffin cups. Freeze until completely frozen, about 6 hours. Remove from muffin cups, and place into two 1-gallon freezer bags, removing as much air as possible. Freeze up to 3 months.
To make one mug cake, spray microwavable mug (about 12 oz) with cooking spray. Remove paper baking cup from frozen cake batter, and place in bottom of mug. Cut 1 PEEPS Marshmallow Chick in half; cut one half into 4 to 5 pieces, and drop into mug on top of frozen cake batter; reserve remaining half for another mug cake.
Microwave uncovered on high, 45 to 50 seconds, or until cake is set on top and edge pulls away from side of mug. Top with about 1 tablespoon of chocolate frosting. Top with 1 whole PEEPS Marshmallow Chick; Serve.
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