The synthesis and crystal structures of two high valent molybdenum complexes containing trisbenzenethiolatophosphine ligands, [Mo 2 (PS3) 2 (PS3H)] (1) and [Mo(PS3″) 2 ] (2), where PS3=[P(C 6 H 4 -2-S) 3 ] 3− , PS3H=[P(C 6 H 4 -2-S) 2 (C 6 H 4 -2-SH)] 2− , and PS3″=[P(C 6 H 3 -3-Me 3 Si-2-S) 3 ] 3− , are described. Compound 1 is a dimeric Mo(IV) species containing three PS3 ligands with an uncoordinated thiol group. An intramolecular hydrogen bonding S–H⋯S was found in the structure. Two molybdenum ions are bridged by three thiolates. The geometry can be described as two pentagonal bipyramids sharing a triangle face formed by three bridging S atoms. Compound 2 is a Mo(VI) species binding with two tetradentate PS3″ ligands. The eight-coordinate molybdenum center adopts a dodecahedral geometry.