Preheat the oven to 400°F. Spray four 6-ounce ramekins with cooking spray and place them on a rimmed baking sheet.
In a medium, microwave-safe bowl, melt the chocolate and butter with the instant coffee and stir until the coffee dissolves and the ingredients come together. Let cool slightly, about 5 minutes. Whisk in the eggs and granulated sugar. Add the flour, vanilla extract, and salt, whisking just until the ingredients come together.
Portion the batter into the prepared ramekins. Bake until the sides are set and the center of each is still a bit wet, 12 to 14 minutes.
Meanwhile, portion 4 scoops of ice cream on a plate and set back in the freezer.
Once the cakes are out of the oven, let stand for 1 to 2 minutes, then carefully flip each cake onto its own plate, and remove the ramekin. Dust the tops with powdered sugar and top each with a pre-portioned scoop of ice cream. Serve immediately.