The electrochemical behaviour of Na(Et2NCS2) and M(Et2NCS2)(2) (M = NI(II), Pd(II) and Pt(II): Et2NCS2-= diethyldithiocarbamate) as studied by cyclic voltammetry in the acetonitrile-(n-Bu)(4)NBF4 solvent-electrolyte couple at room temperature vs. Ag/Ag+ reference electrode. Constant potential electrolyses of the complexes were carried out at their first oxidation peak potentials and monitored in situ by UV-VIS spectrophotometry. The electrolysis of Ni(Et2NCS2)(2) in solution yielded the dimer of the ligand, (Et2NCS2)(2), and Ni2+(sol) as final products. During this electrochemical process the formation of a Ni(III) complex species as an intermediate has been observed. The electrochemical oxidation of bis(diethyldithiocarbamato) complexes of Pd(II) and Pt(II) yielded [Pd(Et2NCS2)(3)](+) and [Pt(Et2NCS2)(3)](+), respectively.