Preheat oven to 375 degrees F. Adjust the oven rack to the lower middle position. Liberally spray eight (6-ounce) ramekins with nonstick spray and set on a baking sheet or dish.
In a small bowl, stir together 1/3 cup cocoa, brown sugar, and 6 tablespoons sugar, making sure all clumps are broken up; set aside.
In a medium-size bowl, combine remaining 1/3 cup cocoa, butter, and chocolate pieces. Microwave, stopping often to stir, until smoother, approximately 1 to 3 minutes. Set the chocolate mixture aside to cool slightly. Learn different techniques for How To Melt Chocolate.
In a large bowl, whisk together the remaining 6 tablespoons sugar, flour, baking powder, vanilla extract, milk, salt, and egg. Whisk in the cooled melted chocolate mixture until smooth. Divide the batter evenly among the prepared ramekins (about 1/4 cup per ramekins - depending on size of your ramekins - do not overfill the ramekins) and smooth the tops. Sprinkle approximately 2 tablespoons of the cocoa/sugar mixture over the top of the batter in each ramekin (should cover the batter completely).
In a small bowl, whisk together the instant coffee, prepared coffee, and water. Heat the coffee mixture in the microwave until hot. Gently spoon approximately 2 to 3 tablespoons of the hot coffee mixture over the top of each ramekin (do not stir).
Bake for approximately 20 minutes or until the cakes are puffed, bubbling, and starting to pull away from the sides of the ramekins. You will see that a crust has formed on the top with a pool of gooey sauce bubbling underneath.
NOTE: It is critical to bake these cakes for the right amount of time. Otherwise, they will either be way too "molten," or end up as brownies. Oven temperatures vary, so check the cakes after 15 minutes. If they are really moist on top, bake one additional minute and check again.
Remove from oven and let the cakes cool for approximately 10 to 15 minutes before serving. This allows the sauce to thicken up to pudding consistency before serving. The cakes will fall (sink) slightly as they cool. May be served warm or at room temperature. I, personally like this cake served warm.
Serve with vanilla or coffee ice cream or whipped cream.
Leftovers can be reheated, covered with plastic wrap, in a microwave oven.
Hot Chocolate Fudge Pudding Cake Recipe: https://whatscookingamerica.net/cake/hotfudgepuddingcake.htm