The catalysts of transition metals (Fe, Co, Ni, Cu, Cr) doped cryptomelane-type manganese oxide (M-OMS-2) were prepared and investigated for the catalytic combustion of dimethyl ether (DME). The catalysts were characterized by XRD, FT-IR, BET, TEM, ICP-AES, XPS and H2-TPR techniques. The effects of surface area, the average oxidation state, and the redox properties on catalytic activities were studied. The results showed that 100% CO2 selectivity can be realized over the doped OMS-2 catalysts. The M-OMS-2 catalysts displayed the nanorod morphology with a 13nm diameter and the length ranging from 50 to 220nm. The Cu doped OMS-2 catalyst exhibited the best activity, achieving the light-off temperature (the temperature acquired for 10% DME conversion, T10) and full-conversion temperature (the temperature acquired for 90% DME conversion, T90) of 171 and 180°C, respectively. DME catalytic combustion over M- OMS-2 catalysts was found to follow a Mars–van-Krevelen mechanism with the presence of redox between Mn4+/Mn3+ and Mm+/M(m−1)+ (M=Fe, Co, Ni, Cu, Cr).