Ba0.95Ce0.8Ho0.2O3-α was prepared by high temperature solid-state reaction. X-ray diffraction (XRD) pattern showed that the material was of a single perovskite-type orthorhombic phase. Using the material as solid electrolyte and porous platinum as electrodes, the measurements of ionic transport number and conductivity of Ba0.95Ce0.8Ho0.2O3-α were performed by gas concentration cell and ac impedance spectroscopy methods in the temperature range of 600-1000 ℃ in wet hydrogen, dry and wet air respectively. Ionic conduction of the material was investigated and compared with that of BaCe0.8Ho0.2O3-α. The results indicated that Ba0.95Ce0.8Ho0.2O3-α was a pure protonic conductor with the protonic transport number of 1 during 600-700 ℃ in wet hydrogen, a mixed conductor of protons and electrons with the protonic transport number of 0.97-0.93 in 800-1000 ℃. But BaCe0.8Ho0.2O3-α was almost a pure protonic conductor with the protonic transport number of 1 in 600-900 ℃ and 0.99 at 1000 ℃ in wet hydrogen. In dry air and in the temperature range of 600-1000 ℃, they were both mixed conductors of oxide ions and electronic holes, and the oxide-ionic transport numbers were 0.24-0.33 and 0.17-0.30 respectively. In wet air and in the temperature range of 600-1000 ℃, they were both mixed conductors of protons, oxide ions and electronic holes, the protonic transport numbers were 0.11-0.00 and 0.09-0.01 respectively, and the oxide-ionic transport numbers were 0.41-0.33 and 0.27-0.30 respectively. Protonic conductivity of Ba0.95Ce0.8Ho0.2O3-α in both wet hydrogen and wet air was higher than that of BaCe0.8Ho0.2O3-α in 600-800 ℃, but lower in 900-1000 ℃. Oxide-ionic conductivity of the material was higher than that of BaCe0.8Ho0.2O3-α in both dry air and wet air in 600-1000 ℃.