A series of copper doped manganese oxide octahedral molecular sieves (Cu-OMSx-T) with different Cu/Mn ratios and hydrothermal temperatures were successfully synthesized and used for catalytic ozonation towards oxalic acid (OA) degradation. The as-prepared Cu-OMSx-T composites were comprehensively investigated by BET, FT-IR, XPS and etc. characterizations. The results indicated that the Cu doping would increase the specific surface area, change chemical bonds, and promote the transformation of multivalent metals and the generation of oxygen vacancies. It was noteworthy that the hydrothermal temperature played an important role in the morphology of Cu-OMSx-T composites and the Cu/Mn molar ratios greatly influenced the catalytic activities. Amongst, the Cu-OMS0.5-140 achieved the optimum catalytic activity with 97.3% of OA degradation efficiency and 98.8% of mineralization rate in 30 min at pH 6.0. Moreover, hydroxyl radical and superoxide radical were identified as the major reactive radicals and the catalytic mechanism for OA degradation enhancement was also elucidated. In addition, the Cu-OMS0.5-140 exhibited great stability and reusability with high OA mineralization rate (> 90%) and low metal release after five times recycle. Overall, the results indicated that the synthesized Cu-OMS0.5-140 is an efficient, stable, and recyclable ozonation catalyst, and could be a promising alternative material for water purification.