Preheat the oven to 350 degrees F. Oil a 9x13 baking pan well and line the bottom with parchment paper so the cake lifts out easily.
Rub the orange zest into the granulated sugar with your fingertips for about 30 seconds, until the sugar smells like orange. This releases the citrus oils and gives you the best flavor.
Add the flour, cocoa powder, baking soda, baking powder, and salt to the sugar and whisk together. If using a stand mixer, use the fitted bowl for the dry ingredients.
In another bowl or large liquid measuring cup, whisk together the eggs, milk, oil, vanilla, and orange juice. Leave out the boiling water, it goes in at the end.
With the mixer on low, slowly add the wet ingredients to the dry. Scrape down the sides and bottom of the bowl. Turn to medium for about 30 seconds, then back to low.
With the mixer on low, slowly add the boiling water. The batter will be very thin and glossy, and that's exactly how it should be.
Pour into the prepared pan and bake for 30 minutes, until the cake has risen in the center and a toothpick comes out with a few moist crumbs. Start checking at 25 minutes.
Cool completely in the pan before frosting.
Chocolate Orange Sour Cream
Over low heat, melt the butter and bittersweet chocolate together in a small saucepan until smooth.
Pour into an electric mixer fitted with the whisk attachment on low speed.
Add the vanilla and powdered sugar and whisk. It will get very thick, but keep whisking. Scrape the bottom of the bowl so you don't end up with lumps of chocolate.
Add the sour cream, orange juice, and orange zest, and whisk until smooth. It may curdle; just whisk right through it, and it will come back together glossy.
Once the cake is completely cool, spread the frosting over the top.
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Notes
Rub the orange zest into the sugar before adding the other dry ingredients. It's the single best thing you can do for the flavor of this cake.Oil and grease your pan well and use parchment on the bottom for easy removal.Mix well but don't overmix. Keep the mixer on low most of the time and scrape the bowl.For a darker cake, use Hershey's Special Dark cocoa powder. Sift it in if it's clumpy.Baking times vary, so set your timer 5 minutes early and check.You'll need about 6 large navel oranges total for the cake and frosting. Zest before you juice.Pan OptionsBundt pan: grease very well, fill two-thirds, bake 40 to 50 minutes.Two 8-inch rounds: bake 25 to 30 minutes. Make the full frosting recipe rather than this half batch.Cupcakes: fill liners two-thirds full and bake about 15 minutes. Makes about 24.How to StoreCounter: covered, up to 2 days.Refrigerate: up to 4 days in an airtight container. Let slices come to room temperature before serving.Freeze: up to 3 months. Freeze unfrosted, wrapped in plastic and then foil. Thaw overnight in the fridge and frost the day you serve.