In this paper, we report a quick approach to self-assemble three-dimensional (3D) spongiform nanofiber stacks via electrospinning, which usually fabricates 2D non-woven fiber mats. Through controlling experimental conditions, cone-like polystyrene fiber stacks can be self-assembled on aluminum foil within 30 min. The stacks are able to reach a height of more than 10 cm. Moreover, conversion between the 3D fiber stack and 2D thin film can be controlled. The formation mechanism of the self-assembled fiber stacks and the influence of experimental conditions have also been explored. The 3D fiber stacks may be promising for applications in many fields such as tissue engineering, electrodes of battery, and filtration, etc.