Bi 2 O 3 -doped ceria oxygen-ion conductors were prepared by a wet chemical synthesis method, which is performed by polymerization of polyvinyl-alcohol (PVA). The experiments showed that Bi 2 O 3 –CeO 2 solid solution with 9.2nm grains and pure fluorite type phase can be synthesized at a calcination temperature of 500°C by PVA polymerization process. X-ray analysis revealed that high density nanostructured bulks could be prepared at a sintering temperature of 900°C, and these bulk samples with an average grain size less than 70nm could effectively be obtained at various heating rates during sintering. Oxygen-ion conductivity increased with the increase of dopant concentrations between 5mol% and 15mol% in present study.