Zinc oxide, a direct band gap semiconductor of ≥3.30 eV, is prevalent in potential requests for energy devices. The early-stage demonstration of ZnO provides a new method of developing high ionic conductivity in multifunctional semiconductors for electrolyte applications in ceramic fuel cells (CFCs). In the present work, we successfully synthesized Na-doped ZnO nanorods by a hydrothermal method and employed them as an electrolyte in CFCs. The synthesized Na-doped-ZnO nanorods showed an effective ionic conductivity of 8.75 × 10−2 S cm−1 along with an excellent power density of 609 mWcm−2 ± 5% when the fuel cell was operating at 550 °C. The enhanced ionic conductivity could be due to Na+ doping into Zn2+ and the high ionic radius of Na ions producing bulk oxygen vacancies in the ZnO structure to conduct oxygen ions or protons. Furthermore, we used experimental analysis, such as X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), ultraviolet–visible (UV–visible), X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS), to evaluate the change in structural properties and mechanism of ionic transport in ZnO nanorods with sodium doping. The presented work provides insight into a novel approach of developing the high ionic conductivity of electrolytes in a low-cost ZnO semiconductor material.