Barium cerate is viewed as one of the advanced high temperature proton conductors, while the chemical stability of such a material is vulnerable in air at high temperatures. In this work, a double-layer electrolyte membrane was prepared by dip-coating an additional layer of BaZr0.8Y0.2O3-delta (BZY2) on a BaCe0.8Y0.2O3-delta (BCY2) layer. The effects of the additional BZY2 layer on the phase composition, the electrolyte morphology and the electrical properties of whole electrolyte membrane have been systematically investigated. The results showed that the double-layer electrolyte membrane had a layered structure. The anode-supported single cell using this double layer electrolyte exhibited a greatly improved chemical stability. These results demonstrated that this double layer electrolyte had a great potential to be used as a stable proton conductor with an acceptable conductivity for reversible solid oxide cells (RSOCs).