Hierarchical layer-stacking Mn-Ce composite oxide with mesoporous structure was firstly prepared by a simple precipitation/decomposition procedure with oxalate precursor and the complete catalytic oxidation of VOCs(benzene, toluene and ethyl acetate) were examined. The Mn-Ce oxalate precursor was obtained from metal salt and oxalic acid without any additives. The resulting materials were characterized by X-ray diffraction(XRD), Brunauer-Emmett-Teller(BET), scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDX), hydrogen temperature programmed reduction(H2-TPR) and X-ray photoelectron spectroscopy(XPS). Compared with Mn-Ce composite oxide synthesized through a traditional method(Na2CO3 route), the hierarchical layer-stacking Mn-Ce composite oxide exhibited higher catalytic activity in the complete oxidation of volatile organic compounds(VOCs). By means of testing, the data revealed that the hierarchical layer-stacking Mn-Ce composite oxide possessed superior physiochemical properties such as good low-temperature reducibility, high manganese oxidation state and rich adsorbed surface oxygen species which resulted in the enhancement of catalytic abilities. Hierarchical layer-stacking Mn-Ce composite oxide with mesoporous structure was pre- prepared by a simple precipitation / decomposition procedure with oxalate precursor and the complete catalytic oxidation of VOCs (benzene, toluene and ethyl acetate) were examined. The Mn-Ce oxalate precursor was obtained from metal salt and oxalic acid without any additives. The resulting materials were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy Compared with Mn-Ce composite oxide synthesized through a traditional method (Na2CO3 route), the hierarchical layer-stacking Mn-Ce composite oxide exhibits higher catalytic activity in the complete oxidation of volatile organic compounds (VOCs). By means of testing, the data revealed that the hierarchical layer-stacking Mn-Ce composite oxide possessed superior physio chemical properties such as good low-temperature reducibility, high manganese oxidation state and rich adsorbed surface oxygen species which resulted in the enhancement of catalytic abilities.