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Preheat the oven to 350 degrees. Spray 2 (8-inch) round cake pans with cooking spray. (Be sure your pans are at least 2 inches tall, because the cake layers rise quite a bit.) Line the bottom of the pans with parchment paper, then spray the paper with cooking spray.
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Combine the cake mix, flour, sugar, sour cream, water, vegetable oil, egg whites, and vanilla extract in a large mixing bowl.
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Beat with an electric mixer on medium speed for 2 minutes—the batter should be very smooth. Use a rubber spatula to scrape up from the bottom and get everything totally mixed together.
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Divide cake batter between the prepared pans and bake cake layers 43 to 48 minutes, until a cake tester inserted into the center of the cakes comes out clean.
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Cool cake layers in the pans for 20 minutes, then carefully transfer to a wire rack to cool completely.
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Once the cake layers are fully cooled, use a long serrated knife to trim them if they’ve domed.
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Use a fork with large tines to poke holes in the cake every half inch or so; try not to go all the way to the bottom of the cake. (If you don’t have a large-tined fork, you can use a toothpick but you'll want to swirl the toothpick around a bit to enlarge some of the holes.)
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Combine the jello and boiling water in a small bowl and stir until the jello dissolves. Set aside to cool for 5 minutes.
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Pour half of the jello over each cake layer. (To avoid a mess on your counters, set the cakes on a wire rack and set the wire rack over a large baking sheet. That should contain any spilled jello.)
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Refrigerate the cake layers for at least 4 hours. You can also refrigerate them overnight, but you should cover them loosely with plastic wrap if you do.