Catalytic combustion of dimethyl ether (DME) over hexaaluminate catalyst BaNi0.2Mn0.8Al11O19-δ has been investigated. The catalysts were prepared with the sol-gel method and reverse microemulsion method respectively and characterized by thermogravimetry-differential thermal analysis, X-ray diffraction and transimission electron microscope. It was found that the formation of Mn, Ni modified hexaaluminate was a relatively slow process via two solid state reactions and spinel structure was a transition phase. At the same calcined temperature and time, the catalyst prepared with the reverse microemulsion method could form the hexaaluminate phase more easily than that prepared with the sol-gel method. The catalyst BaNi0.2Mn0.8Al11O19-δ prepared with the reverse micro-emulsion method appeared a plate-like morphology, while it appeared a needle-like morphology when using the sol-gel method. The catalytic activities of catalysts BaNi0.2Mn0.8Al11O19-δ prepared with two different methods for DME combustion were tested. It showed that catalyst prepared with the reverse microemulsion method had better catalytic activity, i. e. T10% of DME had decreased by 45℃, about 90% conversion of diemthyl ether at 380℃.