Reactions of the previously reported dinuclear vanadium(III) thiolate anion [V-2(edt)(4)](2-) (edtH(2) = ethane-1,2- dithiol) are described. Treatment of (NEt(4))(2)[V-2(edt)(4)] (1) in MeCN with equimolar (C12H8S2)BF4 (C12H8S2+ = the thianthrenium radical cation) results in a one-electron oxidation and isolation of the V-III,V-IV complex (NEt(4))[V-2(edt)(4)] (2). The same product can also be obtained by controlled-potential electrolysis of 1 at -0.20 V vs Ag/AgCl. Treatment of 1 in CH2Cl2, with py gives no reaction, but addition of Me(3)SiCl leads to formation of the known V2OCl4(py)(6) (3). The latter is also formed by the reduction of a 1:1 mixture of VOCl3 and VCl3(THF)(3) in CH2Cl2/py and by the reaction in CH2Cl2 of VCl3(THF)(3) and py with edt(2-). Treatment of 1 in MeCN with bpy (2,2’-bipyridine) gives no reaction, but addition of Me(3)SiCl results in formation and isolation of [V7OCl2(bpy)(4)]Cl-2 (4) identified by spectroscopic comparison with literature data. The reaction of 1 in MeCN with equimolar VCl3(THF)(3) and NEt(4)Cl gives (NEt(4))(3)[V3Cl6(edt)(3)] (5).