Foam-based materials with good light transmission characteristics may be a potential industrial catalyst for photothermal degradation of volatile organic compounds (VOCs). Herein, we designed a novel monolithic catalyst that used Cu foam (CF) as support and loaded Co₃O₄ on the surface to photothermal catalytic oxidation of toluene. The Co₃O₄@CuO_x/CF catalyst displays the remarkable catalytic activity with the maximum toluene conversion of 98% and CO₂ yield of 80% under illumination of 750 mW/cm2 light intensity. Besides, it also shows excellent water resistance, with activity almost unaffected by 10 vol% water vapor. Multiple characterizations reveal that the abundant lattice oxygen and strong light absorption caused by strong interaction between Cu and Co are the main reasons for good photothermal catalytic performance of Co₃O₄@CuO_x/CF. This work provides a reference for the practical industrial application of monolithic catalyst in photothermal catalytic oxidation of VOCs.