We have investigated the valence band structure of MoS2, a transition-metal dichalcogenide, using scannino tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) for the first time. We have found characteristic peaks in the (dl/dV)/(I/V)-V characteristic at −1.0 and −1.4V below the fermi level, which correspond to the S Pz state and Mo dz2 state, respectively. Mo atoms are accessible only at the sampfe voltage of −1.4V in the range of −1.0 through − 1.5V, due to the strong localization of the Mo dz2 state with very small bandwidth.