The catalytic oxidation of binary VOC mixtures, ethyl acetate, and butyl acetate, and the effect of water vapor on their oxidation, was studied over manganese oxide–cryptomelane‐type catalyst. This catalyst, prepared by a novel solid‐state reaction with ball milling, was shown to be very active for the oxidation of ethyl acetate and butyl acetate, promoting their complete oxidation at relatively low temperatures, the CO2 yield being influenced by the type of VOC. The mixture with equal amounts of each ester shows a light‐off curve similar to that observed for butyl acetate alone, but the light‐off curves are shifted to higher temperatures when different proportions of these VOCs are present in the mixture. When processing VOC mixtures, the temperature required for 100% CO2 yield depends on the VOC, which is in larger amount. Water vapor also has a significant effect on the oxidation of these VOCs, particularly in the case of ethyl acetate. © 2016 American Institute of Chemical Engineers Environ Prog, 35: 1324–1329, 2016