The development of highly efficient and stable monolithic catalysts is essential for the removal of volatile organic compounds (VOCs). Copper foam (CF) is a potential ideal carrier for monolithic catalysts, but its low surface area is not conducive to dispersion of active species, thus reducing the interface interaction with active species. Herein, a vertically oriented Cu(OH)2 nanorod was in situ grown on the CF, which acted as the template and precursor to synthesize CoCu-MOF. The optimized catalyst (12CoCu-R) delivers excellent performance for acetone oxidation with a T90 of 195 °C. Impressively, the catalyst demonstrated satisfactory stability in long-term, cycle, water resistance, and high airspeed tests. Therefore, the present study provides a novel strategy for rationally designing efficient monolithic catalysts for VOC oxidation and other environmental applications.