Polarized S K-and L-edge, Mo L 3-and L2-edge x-ray absorption near-edge structure (XANES) of natural molybdenite (2H-MoS2) have been measured with synchrotron radiation. These results are qualitatively interpreted using the energy band model of molybdenite and provide important information on the unoccupied states of molybdenite. The valence band (VB) maximum of molybdenite is characterized by fully occupied Mo 4dz2, and the conduction band (CB) minimum of molybdenite is characterized by unoccupied Mo 4d states. The unoccupied Mo 4 d band is split into two sub-bands, designated as tzg/t+g and eg/e + sets. Although the relative energy of these two sets are difficult to be evaluated, probably the former has the lower energy than the latter, both two sets have the combination wave functions of the other unoccupied Mo 4d components, rather than the simple 4dx2_y2 and 4dxy states. The unoccupied Mo 4d sub-bands contain significant DOS of both S 3p-and 3 s-like states, indicating strong hybridization with S 3 s and 3 p states. In the lower energy sub-band, the DOS of the S Pz-and px.y-like states are very similar. However, in the higher energy sub-band, the DOS of the S 3px, y-like state is lower than that of the S 3pz state. Polarized S K-edge XANES also reveal the features of antibonding S Pz-and px, y-like states in molybdenite. The feature assigned to the S 3pz-like states is stronger and sharper, and shifts to lower energy by about 2 eV relative to that for the S 3 px, y-like states.