Photoelectrochemical biofuel cells can convert light and chemical energy into electrical energy using a dye-sensitized titania (TiO2) fluorine-doped tin oxide photoanode and a platinum-coated fluorine-doped tin oxide cathode. TiO2 of the photoanode serves both as a support for dyes and as an electron-transporting medium, the structure of which can limit electron trapping and charge transporting and then affect the performance of the photoelectrochemical biofuel cells. TiO2 nanotube array films have been shown to enhance the efficiencies of both charge collection and electron injection, and hence a vertically aligned TiO2 nanotube array is investigated as a conductor for the tetrakis(4-carboxyphenyl)porphyrin dye to construct a new two-compartment photoelectrochemical biofuel cell. The photoelectrochemical biofuel cell containing the TiO2 nanotube array photoanode yields a short-circuit (Isc) current of 110 μA and an open-circuit (Voc) potential of 1010 mV. In contrast, the photovoltaic parameters, Isc and Voc of the photoelectrochemical biofuel cell with the mesoporous TiO2 nanocrystal fluorine-doped tin oxide photoanode, are 96.96 μA and 740 mV, respectively. Photovoltaic measurements show that the maximum incident photon-to-collected electron conversion efficiency was 58% at 430 nm through the spectral range (400–800 nm) for the photoelectrochemical biofuel cell with the TiO2 nanotube array fluorine-doped tin oxide photoanode. These results revealed that the TiO2 nanotube array had great potential for the photoelectrochemical biofuel cells.