Four new complexes of the general formula [Ni(SS)(NN)], Where SS is dddt (5, 6-dihydro-1, 4-dithiin-2, 3-dithiolate) or pddt(6, 7-dihydro-SH-1, 4-dithiepin-2, 3-dithiolate) and NN is bpy or phen were prepared. The UV/Vis. Spectra exhibit intense intramolecular ligand-to-ligand charge transfer bands ca. 600 nm. Cyclic voltammetry shows a reversible oxidation step assigned to [Ni(SS) (NN)]0= [Ni(SS)(NN)]+. When the complex [Ni(dddt)(bpy) ] was partially oxidized by [Ni(SS) (NN)]0= [Ni(SS)(NN)]+. When the complex [Ni(dddt)(bpy) ] was partially oxidized by Ⅰ2, a broad ESR signal at g = 2. 003 appeared