Three aggregates of V 2 O 2 (μ-S) 2 units, (Et 4 N) 3 {[V 2 S 2 O 2 (Et 2 dtc) 2 ] 2 K} (1), (Et 4 N) 2 (NH 4 ){[V 2 S 2 O 2 (C 5 H 10 dtc) 2 ] 2 Na} (2), and (Et 4 N) 3 {[V 2 S 2 O 2 (Me 2 dtc) 2 ] 3 Na 3 (H 2 O)} (3) together with a mononuclear complex vanadium tri-pentamethylenedithiocarbamate have been obtained from a reaction system consisting of (NH 4 ) 3 VS 4 , R 2 dtcNa (K) and PPh 3 in CH 3 CN and structurally characterized. All the [V 2 S 2 O 2 (R 2 dtc) 2 ] 2− moieties possess very similar structure parameters and link each other by the interaction between V 2 O 2 (μ-S) 2 units and alkali metal ion, which exists in O and S coordination sphere with coordinate number of 4, 5 or 6, respectively, for the three aggregate complexes. Infra red spectra of these aggregates exhibit the additional coordination of the VO group to alkali metal, leading to red shift of the VO stretch frequency. The 1 H NMR signals of α-CH 2 in the R 2 dtc ligands were observed to be close to those of the R 2 dtcNa, indicating the spin–spin coupling between both V(IV) sites in the [V 2 S 2 O 2 (R 2 dtc) 2 ] 2− moiety. The 51 V NMR signals were observed at approximately 350 ppm. The cyclic voltammogram displays quasi-reversible couple at −0.60 to −0.73 V and an irreversible oxidation at 0.5–0.73 V, responsible for 3-/2-couple redox and 2- to 1- oxidation, respectively, of the [V 2 S 2 O 2 (R 2 dtc) 2 ] 2− moieties. Variable-temperature magnetic susceptibility study exhibits strong antiferromagnetic exchange interactions existing between the two V(IV) sites in the V 2 O 2 (μ-S) 2 units.