H-2-mesoporphyrin IX and Zn-mesoporphyrin IX have been investigated as sensitizers for the titanium dioxide (TiO2) film electrode to construct a new two-compartment photoelectrochemical biofuel cell (PEBFC). The PEBFC can convert the light and chemical energy to electricity by consuming photons and oxidizing glucose. The two sensitizers are similar with two carboxyl anchoring groups, except that the central hydrogen atoms in the Ha-mesoporphyrin IX are replaced by zinc. To determine how cell performance is affected by the sensitizer, we analyze the photochemical and photoelectrochemical properties of the two sensitizers by physical characterization and photoelectrochemical experiments. The UV-Vis absorption spectra and X-ray photoelectron spectra (XPS) indicate that the interactions between the sensitizer and TiO2 decrease in the order of H-2-mesoporphyrin IX > Zn-mesoporphyrin IX. The interactions are also determined by Fourier transform infrared (FUR) spectra which indicate that the two sensitizers are adsorbed on the TiO2 film through the carboxyl groups. The photovoltaic characteristics show the Zn-mesoporphyrin IX is less effective in comparison with the H-2-mesoporphyrin IX, since the Zn-mesoporphyrin IX enhances the back electron-transfer process, producing lower IPCE and current. These results reveal that the H-2-mesoporphyrin IX is a more efficient sensitizer compared with the Zn-mesoporphyrin IX for the PEBFC. Crown Copyright (C) 2012 Published by Elsevier B.V. All rights reserved.