MOFs have been widely used as templates to design and construct catalysis materials, such as LDH, metal oxides, and carbon. Herein, we developed a Cu-mediated pyrolysis protocol for the synthesis of urchin-like CuOx/Fe2O3 hybrid nanostructures using Fe-MOFs as the precursor. The hierarchical hybrids were composed of an inner CuOx-dispersed Fe2O3 octahedral matrix covered with radially grown Fe2O3 nanorods. This novel hierarchical hybrid nanostructure was generated likely due to the difference in the inward contraction rates between the Cu and Fe species during pyrolysis. Given the structural and compositional benefits, the urchin-like CuOx/Fe2O3 hybrids exhibited outstanding catalytic activity for the chemical reduction of 4-nitrophenol (4-NP) and dyes. Besides, CuOx/Fe2O3 was found to be highly catalytic in the reduction of 4-NP even after 30 consecutive runs, manifesting outstanding durability for continuous operation.