Proton ceramic fuel cells (PCFCs) are a better alternative to the combustion-based electrical generators because of their high energy conversion efficiency and low carbon emission at relatively low operating temperatures. The electrochemical performance of PCFCs in terms of conductivity, cycling stability, and power density is heavily influenced by the morphological and compositional characteristics of the electrolyte materials. These characteristics can be controlled during the synthesis and fabrication processes. Microstructural modification of the proton ceramic electrolyte can further optimize the electrochemical performance and enhance the efficiency of PCFCs. The well-known electrolyte materials derived from cerate–zirconate ceramic perovskite-type oxides show incredibly high proton conductivity in hydrogen- and/or water-containing atmospheres. This review aims to discuss the influence of electrolyte synthesis and fabrication techniques on the electrochemical properties of PCFCs. Results and findings from different studies are explored and analyzed to examine the effects of grain size, sample density, sintering temperatures, and the addition of metal oxides on the electrolyte performance of PCFCs.