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The detailed synthesis and characterization of four ruthenium(II) complexes [RuLL′(NCS)2] is reported, in which L represents a 2,2′-bipyridine ligand functionalized at the 4,4′ positions with benzo[1,2- b:4,5- b′]dithiophene derivatives (BDT) and L′ is 2,2′-bipyridine-4,4′-dicarboxylic acid unit (dcbpy) (NCS=isothiocyanate). The reaction conditions were adapted and optimized for the preparation of these amphiphilic complexes with a strong lipophilic character. The photovoltaic performances of these complexes were tested in TiO2 dye-sensitized solar cell (DSSC) achieving efficiencies in the range of 3-4.5 % under simulated one sun illumination (AM1.5G). [ABSTRACT FROM AUTHOR]