Vanadium(III) thiolate complexes carrying a phenoxide-based tridentate ligand were prepared from the reactions of V(NMe2)4 with the protonated forms of tridentate ligands (H2(O,P,O) = bis(3,5-di-tert-butyl-2-hydroxyphenyl)phenylphosphine or H2(O,O,O) = bis(3,5-di-tert-butyl-2-hydroxyphenyl)phenylphosphineoxide) and thiols (HSR; R = mesityl (Mes), 2,4,6-(i)Pr3C6H2 (Tip)). The vanadium-thiolate complexes were subjected to the V/Fe/S cluster synthesis via treatment with an Fe(II) thiolate complex [(TipS)Fe]2(μ-SDmp)2 (4, Dmp = 2,6-(mesityl)2C6H3) and elemental sulfur in toluene, leading to the formation of two new V/Fe/S clusters. One is an edge-bridged double-cubane-type [VFe3S4]-[VFe3S4] cluster [(O,P,O)VFe3S4(SDmp)(HNMe2)]2 (5) having face-capping tridentate (O,P,O) ligands on vanadium atoms. The other is a [VFe3S4-Fe] cluster [(μ-O,O,O)VFe3S4(SDmp)(STip)Fe(μ-SDmp)] (6), the core of which consists of a cubane-type [VFe3S4] unit and an external iron atom. The external iron is bound to an SDmp ligand and two oxygen atoms of the tridentate (O,O,O) ligand. Cluster 6 is structurally relevant to the active site of nickel-dependent CO dehydrogenase, and their common structural features include a cubane-type unit with a heterometal, one more iron atom besides the cubane unit, and a bridging ligand between the external iron and the heterometal of the cubane unit.