Reaction of [(Me3Si)(2)N](2)VCl(THF) with S-8 led to the formation of the dinuclear and diamagnetic complex {[(Me3Si)(2)N](2)V}(2)(mu-S)(2) (1), whose connectivity was elucidated by an X-ray crystal structure. Ab initio theoretical calculations carried out on both complex 1 and the isostructural oxo-bridged dimer indicated a determinant participation of the bridging atoms in the formation of V-V bonds. Crystal data for 1 are as follows : C24H72N4- Si8V2S2, fw 807.54, monoclinic P2(1)/c, a = 9.1356(2) Angstrom, b = 14.5955(3) Angstrom, c = 34.8578(6) Angstrom, beta = 95.744(1)degrees, V = 4626.1(1) Angstrom(3), Z = 4, T = -153 degrees C.