The cis-[Ru(dppb)(Me-bipy)(NCS)(2)], dppb = 1,4-bis (diphenylphosphino)butane, Me-bipy = 4,4'-dimethyl-2,2'-bipyridine, and NCS = thiocyanate, was synthesized and characterized by spectroscopic and electrochemical techniques and its structure was determined by crystal X-ray analysis. The crystal structure reveals that the coordination geometry around the Ru(II) center is distorted octahedron where two molecules of thiocyanate are bonded to the ruthenium through nitrogen atom in cis orientation. The half-wave formal potential value E-1/2 = 0.8 V (versus Ag/AgCl) observed is considerable higher than that for the cis-[RuCl2(dppb)(Me-bipy)] complex, E-1/2 = 0.6 V (versus Ag/AgCl), well illustrating the strong pi-acceptor effect the NCS ligand toward the backbonding interaction with the Ru(11) metal center. The MLCT absorption bands of the thiocyanate complex present a higher molar absorptivity (about 12%) compared with the cis- [RuCl2(dppb)(Me-bipy)] complex, in the same experimental conditions. These properties make the complex potentially promising for the photosensitization process.