Doped ceria has been pursued in the past decades as a promising electrolyte material for intermediate temperature-solid oxide fuel cells. In this study, the effects of grain growth conditions on the densification and conductivity of CaxCe1-xO2-y (x=0.05, 0.1, and 0.2) are systematically investigated. It has been found that the densification of Ca-doped CeO2 depends strongly upon the specific calcination and sintering pathway, based on which the processing windows for achieving high sintering density are established. It is demonstrated that Ca-doped CeO2 show competing conductivities in the intermediate temperature region compared with rare earth-doped CeO2. The detailed microstructures associated with various processing pathways have also been realized in terms of microdomain, superstructure, and glassy phase.