The surface composition and electronic structure of tungsten carbides prepared by directsynthesis and carburization of white tungstic acid were studied with x-ray photoelectron spectroscopy.The experimental results show that WO_3 and free carbon were present on the surface of the carbides.For the high surface area tungsten carbide prpared from white tungstic acid,a large extent ofoxygen insertion into the crystal lattice was observed.The measurements of the binding energies of theW_(/2),C_and O_core levels indicate that charge transfer was from W to C and O atoms,formingW_(5d)-C_(2p) and W_(5d)-O_(2p) bonds.The catalytic behavior of the tungsten carbides towards CO hydrogenationwas studied and compared with Group Ⅷ metal eatalysts.