For microsized CaO calcinated from calcium acetate as CO2 sorbent, the CO2 adsorption efficiency increased with the increased of temperature, but decreased when the temperature was over 750 °C, due to the endothermic decomposition of CaCO3. The decreased CO2 partial pressure was unfavourable to CO2 adsorption. The steam reforming of the simulated bio-oil over the Ce–Ni/Co catalyst supported on Al2O3 balls was performed, and the optimal results for hydrogen production were obtained at 700 °C, the S/C ratio of 9 and the LsHSV of 0.23 h−1, with the actual hydrogen yield of 83.8% and the H2(+CO + CH4) yield of 94.1%. In the steam reforming experiment with in continuous situ CO2 capture, the feeding of CaO into the reforming reactor made the hydrogen concentration improved excellently upto 93.3%. However, the H2 yield decreased at higher CaO/C ratio, mainly because the excessive CaO restrained the contact between the reactants and the catalyst. Besides, the higher S/C ratio decreasing the CO2 partial pressure, was against the simultaneous CO2 adsorption, with the optimal S/C ratio of 9.