Two new ruthenium complexes [Ru(dcbpy)(L)(NCS)(2)] where dcbpy is 4,4'-dicarboxylic acid-2,2'-bipyridine and L is 3,8-bis(4-octylthiophen-2-yl)-1,10-phenanthroline (CYC-Pl) or 3,8-bis(4-octyl-5-(4-octylthiophen-2yl)-1,10-phenanthroline (CYC-P2), are synthesized, characterized by physicochemical and semiempirical computational methods, and used asphotosensitizers in nanocrystalline dye-sensitized solar cells. It was found that the difference in light-harvesting ability between CYC-P1. and CYC-P2 is associated mainly with the location of the frontier orbitals, in particular the highest occupied molecular transfer (MLCT) transition, but at the same time reduces the molar absorption coefficient, owing to the HOMO located partially on the ancillary ligand of the ruthenium complex. The incident photon-to-current conversion efficiency curves of the devices are consistent with the MLCT band of the complexes. Therefore, the overall efficiencies of CYC-P1 and CYC-P2 sensitized cells are 6.01 and 3.42 %, respectively, compared to a cis-di(thiocyanato)-bis(2,2'-bipyridyl)-4,4'-dicarboxylate ruthenium(Il)-sensitized device, which is 7.70 % using the same device-fabrication process and measuring parameters.