Preheat the oven to 350ºF (177ºC) and prepare three 6-inch or two 8-inch cake pans by spraying the sides with baking spray and placing a parchment paper circle into the bottom of each one.
In a small jar or liquid measuring cup, whisk together the fresh squeezed orange juice with the whole milk and set aside. The mixture will begin to curdle over the next few minutes, and that chemical reaction is a good thing in this recipe!
Using a stand mixer fitted with the paddle attachment (or a hand mixer with a large bowl), mix together the sugar and orange zest until fragrant and well combined, about 1 minute. Add in the flour, cocoa powder, baking soda, baking powder, and salt. On low speed, mix together with the orange-sugar mixture until combined.
Add the vegetable oil, eggs, vanilla, and orange-milk mixture, then mix on low speed until just combined. With the mixer still on low, add the hot coffee (or hot water!) in a slow stream, then turn the mixer to medium and beat until smooth, about 2 minutes. The batter will be very thin.
Pour into prepared cake pans and bake for 32-36 minutes, until a toothpick inserted comes out clean. Let the layers cool in the pan for about 5 minutes before removing and continuing to cool on a wire rack or flat surface. Cool completely to room temperature before frosting.