A continuous aerosol route is demonstrated for the gas-phase synthesis of the copper-based metal–organic framework (Cu-MOF) supported on CeO2 nanoparticle clusters, which can be used to fabricate MOF-derived Cu@CeO2 hybrid nanomaterials for the catalysis of reversed water–gas shift reaction (RWGS). The results show that both metal surface area and metal dispersion were enhanced by decreasing the Cu/Ce atomic ratio of the hybrid material. Incorporation of the CeO2 nanoparticle cluster enhanced both activity and stability of the MOF-derived nanostructured catalysts. In addition to high selectivity and sufficient operation stability toward RWGS, a superior high catalytic activity under a relatively low-temperature operation was achievable (i.e., TOFCO2 = 0.1635 s–1 at 400 °C) in comparison to the reported values in the literature. The present development for MOF-derived nanostructured materials produced by using an aerosol-based evaporation-induced self-assembly method opens up opportunities for the design of nanostructured catalysts useful for a variety of applications in CO2 capture and utilization.