AbstractSodium silicate was used as a binder to prepare LaCePr oxides (LCP) and La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) thin films on a Ni0.8Co0.15Al0.05Li oxide ceramic substrate for the first time. The microstructure, morphology, and electrical properties of the LSCF–LCP thin films were characterized and investigated by using XRD, SEM, energy‐dispersive X‐ray spectroscopy, and electrochemical impedance spectroscopy. The film sintered at 600 °C presents promising density and has been successfully applied as the electrolyte membrane for solid‐oxide fuel cells (SOFCs). Such a device achieved a respectable electrochemical performance with an open‐circuit voltage of 1.04 V and a maximum power output of 545 mW cm−2 at 575 °C. These findings suggest that sodium silicate is a suitable binder for the preparation of dense thin‐film membranes for SOFCs. Moreover, the preparation technology based on sodium silicate eliminated degumming and high‐temperature sintering, which resulted in greatly simplifying the preparation process of the thin‐film fuel cell towards potential fuel cell commercialization.