We describe the use of a horizontal deposition method to prepare large-area binary colloidal crystals (bCCs). Two different sets of binary polystyrene spheres were employed to demonstrate the validity of this method. By varying the number ratios of small spheres with respect to large spheres, the stoichiometric configuration of the bCCs can be altered. Stable corresponding replica structures of the bCCs were also prepared, and the cross-sectional images of the binary inverse opals were obtained. Optical characterization demonstrated the presence of pseudostop bands, which were in agreement with the compositions of the material. The formation of the bCC by such a simple self-assembly method was attributed to the cooperative effect of interparticle electrostatic interactions and geometrical constrictions. This facile fabrication method further enhances the application potential of the bCCs and their inverse porous replicas with a binary pore system in the fields of photonics, solar cells, separations, catalysis, and biosensing.