Abstract: NiFe₂O₄ possesses high redox activity and oxygen carrying capacity, which shows great potential in the application of two-step thermochemical cycle cracking of CO₂ to produce fuel （CO）. However, NiFe₂O₄ is prone to phase separation at high temperatures, resulting in severe surface sintering, which reduces its redox activity. To address this problem, CeO₂−doped NiFe₂O₄−based composite catalyst materials were synthesized using the ball milling solid phase method and applied to the two-step thermochemical cycle cracking of CO₂ reaction. The effect of CeO₂ doping amount on CO₂ cracking performance was studied by thermogravimetric analysis. The effect of oxidation temperature on the oxidation performance of NiFe₂O₄ and 8NiFe₂O₄−2CeO₂ was investigated based on a fixed bed reactor, and their long-term cycle stability was compared. The mechanism of doping CeO₂ on the performance improvement of NiFe₂O₄−based composite catalyst was explored by various characterization methods （XRD, SEM−BSE, H₂−TPR and XPS）. The results showed that the 8NiFe₂O₄−2CeO₂ composite catalyst exhibited the best redox performance. With the increase of oxidation reaction temperature, the initial reaction rate of NiFe₂O₄ and 8NiFe₂O₄−2CeO₂ became faster and the CO yield increased. When the oxidation temperature was between 800 and 1200 ℃, the CO yield of 8NiFe₂O₄−2CeO₂ was better than that of NiFe₂O₄. In addition, doping CeO₂ can reduce the reduction temperature of Fe element. Compared with pure NiFe₂O₄, the reduction temperature of Fe₃O₄ to FeO in 8NiFe₂O₄−2CeO₂ was reduced by about 6 ℃. Doping CeO₂ can increase the oxygen vacancy concentration of NiFe₂O₄−based catalyst materials. The content of adsorbed oxygen in 8NiFe₂O₄−2CeO₂ was as high as 47.22%, which was much larger than the content of adsorbed oxygen in NiFe₂O₄ （27.44%）. Doping CeO₂ can also significantly improve the spectral absorptivity of NiFe₂O₄ in the near-infrared band. The average solar spectral absorptivity of 8NiFe₂O₄−2CeO₂ was about 88.60%. This work can provide guidance for the development of catalyst materials for the two-step solar thermochemical cracking of CO₂.