The sorption-enhanced steam reforming (SESR) of poplar sawdust pyrolysis oil and acetic acid for high-purity hydrogen production was investigated in this present work. The Ni/CeO2-ZrO2-CaO bifunctional materials with different Ce/Ca ratios were prepared and characterized by the analytic techniques of N2 adsorption desorption measurement, X-ray diffraction, temperature-programmed reduction, temperature-programmed oxidation, and transmission electron microscopy. The effects of the Ce/Ca ratio in Ni/CeO2-ZrO2-CaO catalysts on the CO2 capture abilities and the catalytic behaviors were also discussed. The Ni/CeO2-ZrO2-CaO catalyst showed an excellent catalytic performance with a purity of H2 up to about 95% even after 15 consecutive cycles for the SESR of acetic acid. It also exhibited an improved catalytic activity for the SESR of poplar sawdust pyrolysis oil. However, after several SESR operations of bio-oil, the carbon deposits and Ni particles sintering could be found on the surface, which might be the dominant deactivation cause for this catalyst.