Developing high-performance catalyst is of paramount for NO direct decomposition. Here, composite catalysts BaMnO3-CeO2 were designed and prepared by the one-pot method, which show high catalytic activity, oxygen resistance and durability. The NO conversion to N2 of 85.9% at 800 oC is achieved for 5%BaMnO3-CeO2. It exhibits 66.5% activity in the presence of 10 vol% O2 and runs stable for more than 200 h in 5 vol% O2 at 800 oC. The high performance is originated from the strong interaction between BaMnO3 and CeO2 components, where CeO2 can effectively inhibit the sintering of BaMnO3 particles, enhance the redox activity, mobility of lattice oxygen and NO sorption. The proposed catalytic mechanism based on diffuse reflectance infrared Fourier transform spectroscopy and kinetic study reveals that the formation of N2O* intermediate species is the rate determining step. BaMnO3-CeO2 prepared by the one-pot method can be a promising catalyst candidate for NO direct decomposition.