Density　functional　theory　(DFT)　calculations　are　employed　to　investigate　the　structural　and　electronic　properties　of　MoS6-　and　MoS6　clusters.　Generalized　Koopmans＇　theorem　is　applied　to　predict　the　vertical　detachment　energies　and　simulate　the　photoelectron　spectra　(PES).　Intriguingly,　the　terminal　S2-,　polysulfide　S-2(2-)　and　S-3(2-)　ligands　simultaneously　emerge　in　the　lowest-energy　structure　of　MoS6.　Molecular　orbital　analyses　are　performed　to　analyze　the　chemical　bonding　in　MoS6-/0　clusters　and　elucidate　their　structural　and　electronic　properties.