Two dinuclear oxovanadium(IV) thiolate complexes, [N(C5H11)(4)][VOL1](2) (1) and [N(C4H9)(4)][(VOL2)(2)(mu-OCH3)] (2) (where L1 = [(CH3)SiO(C6H4-2-S)(2)](3-) and L2 = [(C6H5)PO(C6H4-2-S)(2)](2-)), have been synthesized and characterized. The geometry of the anion in 1 can be classified to an edge-sharing bi-square-pyramid with a syn-orthogonal configuration. The one in 2 can be view as a face-sharing bioctahedron with two oxo groups in syn positions. Of note, these two complexes display intramolecular ferromagnetic interaction between two metal centers.