Achieving carbon neutrality is one of the most important tasks to meet the environmental challenges due to excessive CO ₂ emissions. Integrated CO ₂ capture and utilization (ICCU) represents an effective process for direct utilization of CO ₂ -contained exhaust gas (e.g. flue gas), in which converting the captured CO ₂ into CO via reverse water–gas shift (RWGS) reaction is a promising route. The dual functional materials (DFMs), containing CO ₂ adsorbents and catalysts, are widely applied to achieve ICCU. The conventional active metals (Ni, Fe, etc.)-based DFMs and non-transition metal DFMs (e.g. CaO) are restricted by low CO selectivity, catalytic efficiency or CO generation in the CO ₂ capture step. To address the above obstructs in the application of DFMs, the metal oxides-based DFMs, MO _x -CaO (M = Al, Ce, Ti or Zr), are synthesized and evaluated. The CeO ₂ -CaO outperformed the other metal oxides-based DFMs and possessed significantly improved catalytic performance. It is found that 33% CeO ₂ -CaO DFM displayed approximately 49% CO ₂ conversion and approximately 100% CO selectivity in integrated CO ₂ capture and reverse water–gas shift reaction (ICCU-RWGS) at 650°C, while CaO-alone only achieved approximately 20% CO ₂ conversion at the same condition. The surface basicity of CeO ₂ is revealed to contribute to the improved catalytic performance by enhancing CO ₂ chemisorption and activation in the hydrogenation step. Furthermore, CeO ₂ -CaO material possessed excellent cycle stability in 20 cycles ICCU-RWGS, achieving a sustainable and high-efficient performance in CO ₂ conversion and CO selectivity.