Abstract NiMn oxides with different ratios (Ni x Mn y O z ) as well as spinel‐type NiMn 2 O 4 oxides were synthesized and utilized in the catalytic oxidation of toluene. The results indicate that NiMn 2 O x synthesized by the oxygen‐only roasting method exhibits superior catalytic activity due to the appropriate metal valence distribution. The catalytic activity is strongly related with the crystalline phase structures, NiMn 2 O 4 spinel oxides catalyst shows the best low‐temperature performance with 90 % conversion (T 90 ) at 230 °C. Characterization results reveal that the superb catalytic performance of NiMn 2 O 4 spinel oxide is mainly profit by the larger surface area, more abundant surface fugacious oxygen, stronger toluene adsorption capacity than that of the other Ni x Mn y O z catalysts, which in favor of the speedy conversion of benzoic acid, improving the toluene catalytic performance. This finding provides a novel design strategy of NiMn composite oxides for synthesis of high‐efficiency performance toluene catalysts.