Highly crystalline perovskite ceramics were templated by an eggshell membrane (ESM) via strong metal-protein bonding. Templated Sm0.5Sr0.5CoO3 (SSC) ceramics retained an interwoven fibrous structure at a temperature up to 1000 °C. The use of citric acid-assisted sol–gel coating in the template synthesis greatly enhanced the crystallininty of the ceramic because the sol–gel process ensured the stoichiometric adsorption of ceramic precursors, and it also affected ceramic morphology. The highly crystalline SSC ceramic was used as a cathode material of solid oxide fuel cell (SOFC), and the cathode properties were compared with those prepared with the ceramic synthesized via a conventional combustion method. The maximum power density of the cell made with the templated SSC was 44.5% and 29.8% higher than that made with the combusted SSC at 600 °C and 500 °C, respectively, because the highly porous cathode constructed with the templated SSC reduced the cell concentration polarization and cathode polarization resistance. This study suggests high-performance perovskite ceramic for SOFC was produced via the template synthesis.