The hybrid quantum system of cold atomic gas and optical cavity can host many exotic phenomena including phase transitions and multistabilities. In this Letter, we investigate the effect of photon hopping between two Dicke cavities and show rich quantum phases for steady states and dynamic processes. Starting from a generic dimer system where the two cavities are not necessarily identical, we analytically obtain all possible steady-state phases and confirm their existence by numerical calculations. We then focus on the special case where the two cavities are identical, where exact solutions of all phases are obtained. Our results suggest that photon hopping is a convenient and powerful tool to manipulate the quantum phases and induce multistable behavior in this system.