Density　functional　theory　(DFT)　and　coupled　cluster　theory　(CCSD(T))　calculations　were　employed　to　investigate　the　structural　and　electronic　properties　of　NbS6-　and　NbS6-　clusters.　Generalized　Koopmans＇　theorem　was　applied　to　predict　the　vertical　detachment　energies　and　simulate　the　photoelectron　spectra　(PES).　The　current　study　indicated　that　various　types　of　sulfur　ligands　(i.e.,　S2-,　S-2(-),　S-2(2-)　and　S-3(2-))　were　presented　in　the　lowest　-energy　structures　of　NbS6-/0.　The　ground-state　structure　of　NbS6-　is　shown　to　be　C-s　((1)A＇)　symmetry　with　a　terminal　S2-,　a　side-on　bound　S-2(2-)　and　a　S-3(2-)　ligands.　Molecular　orbital　analyses　were　performed　to　analyze　the　chemical　bonding　in　NbS6-/0　clusters　and　elucidate　their　structural　and　electronic　properties.