Herein, we have studied an alternative route for preparing CuOx/CeO2 catalysts using metal organic frameworks (MOFs) as precursors. Usually, CuOx/CeO2 materials are prepared by wet impregnation of ceria support. In this study, we have impregnated a Cu-MOF with a ceria precursor and then pyrolized the impregnated MOF using different conditions and procedures. The prepared catalysts have been characterized by using a wide range of techniques such as XRD, XPS, Raman, and TPR. We have found that the pyrolysis method determines the dispersion of the oxidized copper species on the ceria surface what, in turn, controls the catalytic activity and selectivity of the catalysts in the reverse water-gas shift (RWGS) reaction. We have compared the behavior of the MOF-derived catalysts against an optimized catalyst prepared by a conventional method (wet impregnation), finding that the MOF-derived catalyst shows better catalytic performance.