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A thin Ba3Ca1.18Nb1.82O9−δ (BCN18) membrane electrolyte was prepared by a novel and facile method on a NiO–BCN18 anode substrate. The interesting aspect of the method was the adoption of a in situ reaction of BaCO3, CaCO3, and Nb2O5 on the anode substrate to prepare a dense BCN18 membrane. The BCN18 membrane obtained, which was about 15 μm in thickness and showed high chemical stability against H2O and CO2, attained a high density after sintering at 1400°C. The elemental composition of the BCN18 membrane prepared was identified by energy‐dispersive X‐ray spectroscopy analysis. With La0.7Sr0.3FeO3−σ (LSF) as the cathode, the fuel cell performance with the structure of Ni–BCN18/BCN18/LSF was studied.

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