A crystalline metal organic framework Ni3(BTC)2?12H2O was prepared with solvothermal method. The NiO catalysts with (111) facets exposed were produced from the matrix of Ni3(BTC)2?12H2O,serving as a catalyst for CO oxidation. Comparison of the catalytic performance between the NiO catalysts with (111) facets exposed and the NiO(R) obtained by decomposition of Ni(NO3)2?6H2O was conducted to study the catalytic behavior of the catalysts. The catalysts were characterized with transmission electron microscopy (TEM),X-ray diffraction (XRD),N-2- adsorption- desorption,and X-ray-photoelectron spectrograph(XPS). The results showed that the NiO nanoparticles with (111) facets exposed was well distributed. The activity of catalyst NiO with (111) facets exposed was much higher than that of the NiO (R) obtained by decomposition of Ni(NO3)2?6H2 O catalyst in CO oxidation test,indicating that a crystalline metal organic framework is the suitable candidate for achieving catalyst with exposing special crystal surface.