Highly ordered superlattices assembled from transition metal oxide/sulfide submicrometer particles are difficult to prepare due to lack of monodisperse primary building blocks. In this work, we have successfully synthesized monodisperse Cu2O spheres with diameters in the submicrometer regime of 130 similar to 135 nm. Using the as-prepared Cu2O spheres as solid precursor, uniform hollow CuS and CuSe derivatives have also been synthesized in solution media. More importantly, a ranee of two-dimensional and three-dimensional superlattices of Cu2O, CuS, and CuSe solid/hollow spheres have been assembled for the first time. Without assistance of conventional sacrificing solid templates, the degree of ordering achieved in these superlattices is comparable to those reported for well-studied silica and polystyrene beads. The realization of these self-assembled superlattices may provide a new way of thin film design and fabrication for this class of photosensitive semiconducting materials using their prefabricated building blocks.