A thermally stable 2D array of spheres and their morphology control become important for the fabrication of novel nanostructures. Here, a simple method is presented for fabrication of large-area and well-ordered arrays of carbonized polystyrene (PS) hollow spheres with a controlled (close-packed or non-close-packed hexagonal) morphology, prepared by combining the self-assembly of PS-grafted silica nanoparticles, etching, electron irradiation, and subsequent thermal annealing. Fine control in the 2D or 3D nanostructure of carbon materials can open up new opportunities for high-performance nanoscale applications that require an efficient fabrication method for preparation of the porous carbon array.