We have recently fabricated dye-sensitized solar cells (DSSCs) comprising nanofibrous TiO(2) membranes as electrode materials. A thin TiO(2) film was pre-deposited on fluorine doped tin oxide (FTO) coated conducting glass substrate by immersion in TiF(4) aqueous solution to reduce the electron back-transfer from FTO to the electrolyte. The composite polyvinyl acetate (PVac)/titania nanofibrous membranes can be deposited on the pre-deposited thin TiO(2) film coated FTO by electrospinning of a mixture of PVac and titanium isopropoxide in N,N-dimethylformamide (DMF). The nanofibrous TiO(2) membranes were obtained by calcining the electrospun composite nanofibres of PVac/titania as the precursor. Spectral sensitization of the nanofibrous TiO(2) membranes was carried out with a ruthenium (II) complex, cis-dithiocyanate-N,N(')-bis(2,2(')-bipyridyl-4,4(')-dicarboxylic acid) ruthenium (II) dihydrate. The results indicated that the photocurrent and conversion efficiency of electrodes can be increased with the addition of the pre-deposited TiO(2) film and the adhesion treatment using DMF. Additionally, the dye loading, photocurrent, and efficiency of the electrodes were gradually increased by increasing the average thickness of the nanofibrous TiO(2) membranes. The efficiency of the fibrous TiO(2) photoelectrode with the average membrane thickness of 3.9 µm has a maximum value of 4.14%.