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Preheat the oven to 350°F. Choose your Bundt pan: It should have a 12-cup capacity and be relatively simple in design, like the Original Classic Bundt Pan. (The more complex the design, the more likely the chocoflan is to stick.) Generously spray the pan with nonstick spray and place it inside of a roasting pan.
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To make the caramel: In a small, heavy-bottomed skillet, place the sugar; warm over medium heat. Using a flexible spatula, stir the sugar frequently as it heats, clumps, then melts into an amber-colored caramel. (This process takes about 7 to 10 minutes.) Once all the sugar has melted, immediately transfer it to the bottom of the prepared pan and set aside.
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To make the cake: In a 4-cup capacity liquid measuring cup or medium bowl, combine the water and espresso powder. Stir to dissolve, then whisk in the oil, buttermilk, egg, and vanilla. Set aside.
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In a large mixing bowl, sift the flour, sugar, cocoa powders, baking powder, baking soda, and salt, then whisk to combine.
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Add the wet ingredients to the dry ingredients and whisk to fully incorporate. The batter will be thick. Transfer the batter to the pan and use a spatula to evenly spread it on top of the caramel.
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To make the flan: In the work bowl of a food processor or high-speed blender with at least a 5-cup capacity, combine all of the flan ingredients. Blend until completely smooth, about 25 to 30 seconds.
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Using a ladle or large scoop, very gently spoon the flan mixture on top of the cake batter. Do this step as delicately as possible to avoid mixing the layers of cake and flan together.
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To bake the chocoflan: Cover the Bundt pan loosely with aluminum foil and transfer the roasting pan to the oven. Fill the roasting pan with enough hot water to reach 2" to 3" up the sides of the Bundt pan.
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Bake the chocoflan for 1 hour then remove the foil and let the chocoflan continue to bake for another 40 to 50 minutes. The chocoflan is done when a toothpick or thin knife inserted into the cake near the center comes out mostly clean (some fudgy cake crumbs are OK).
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Remove the Bundt pan from the roasting pan and let the chocoflan cool completely on a cooling rack, about 2 hours. Once cool, loosely cover the chocoflan with the foil and chill in the refrigerator for at least 2 hours or overnight.
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About 1 hour before you'd like to serve the chocoflan, remove it from the refrigerator and let it warm up at room temperature for 30 to 45 minutes. Run an offset spatula or butter knife around the edges and center of the Bundt pan to loosen the cake.
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Place the Bundt pan back into the roasting pan and add enough boiling water to reach about 2" to 3" up the sides of the Bundt pan. Let the chocoflan sit in the hot water for 20 to 25 minutes before inverting it quickly and confidently onto a large serving plate with a rimmed edge. Serve the chocoflan with a drizzle of dulce de leche, if desired. It’s OK if some of the caramel remains in the bottom of the pan.
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Storage information: Keep leftover chocoflan loosely covered with plastic in the refrigerator for up to 3 days; freezing is not recommended.
