A colloidal crystal fabricated from monodispersed mesoporous silica spheres (MMSS) has been employed as a sacrificial template to prepare nanoporous carbon architectures. The mesostructure of MMSS was well replicated, even when they were fabricated to the colloidal crystal, in the nanopores of the carbon spheres. By changing the filtration process slightly, the 3D-packed nanoporous carbon colloidal crystal and the novel "ball in cup" carbon hierarchical structure were successfully obtained.