Hierarchically ordered porous materials have drawn intense attention owing to the drastically enlarged surface area, the defined multiscale porous structure, and the new route of introducing additional functionality. This class of materials present significant potential in the fields of molecular separation, catalysis, micro-reactors, tissue engineering, photonic bandgap (PBG) materials, and phononic bandgap materials. Binary colloidal crystal, a binary crystal structure formed by two sizes of colloidal particles, has proven to be an excellent template for fabricating hierarchically ordered porous materials. In this paper, we demonstrate the horizontal deposition method18 as a facile approach to the growth of bCCs19. The large-area bCCs were subsequently used as templates for forming hierarchical macroporous structures.