A kind of novel composite electrolyte, consisting of zinc doped ceria and carbonates, was developed. The phase and morphology of the composite material were characterized. Ceramic fuel cells based on this composite electrolyte were constructed with two techniques. The hydrogen-air fuel cell fabricated with anode-supported technique showed relative low open circuit voltages (OCVs) and high output performance, but the electrolyte-supported one exhibited relative high OCVs and low output performance. During the fuel cell operation, water was observed at both anode and cathode sides, indicating hybrid ions conduction lies in the composite electrolyte under fuel cell environment.