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-,　S2-,　S22-　and　S32-)　were　presented　in　the　lowest-energy　structures　of　NbS6-/0.　The　ground-state　structure　of　NbS6-　is　shown　to　be　Cs(1A＇)　symmetry　with　a　terminal　S2-,　a　side-on　bound　S22-　and　a　S32-　ligands.　Molecular　orbital　analyses　were　performed　to　analyze　the　chemical　bonding　in　NbS6-/0　clusters　and　elucidate　their　structural　and　electronic　properties.