The multilayered thin film fuel cells (multilayered-TFFCs) using anatase TiO 2 as an anodic catalyst were successfully prepared by layer-by-layer (LbL) assembly technique. The electrode-membrane assembly (MEA) of the multilayered-TFFC, which had a total thickness of approximately 720nm, was constructed on a continuously porous glass substrate. The anode and the cathode were separated by the multilayered polymer electrolyte having a thickness of about 350nm. The amounts of anodic TiO 2 nanoparticles and cathodic Pt nanoparticles were calculated to be 6.2μgcm −2 and 18μgcm −2 , respectively. The open circuit voltage was obtained by ultraviolet (UV) irradiation and methanol supply, because electrons were derived from photocurrent and methanol oxidation. The resultant current densities increased with increasing methanol concentration and intensity of UV irradiation. The multilayered-TFFC with 5molL −1 methanol solution showed the maximum power density of 13μWcm −2 by UV irradiation of 20mWcm −2 .