UPS, XPS, AES and LEED have been applied to study the samples prepared by low energy N+(0.5keV) sputtering slightly the clean cleaved surface of 2H-MoS2 (0001). From UPS (He Ⅰ, He II) spectra the shifts of EF of d band were observed. A "shoulder" or a band tail above the top of the d(z2) band raised with the time of ion bombardment so that the shape of the d(z2) band became broad. The new state showed chemically active to O2 exposure at room temperature. We propose that these shoulder states arise from the new unsaturate bonding d-electrons of Mo atoms around the vacancies of S at the outermost layer of the surface. This new surface electronic state may be correlated with the catalysis active site for hydrodesulfurization (HDS).