Anatase and rutile film electrodes with comparable porosities were prepared by the sol-gel dip-coating method, and the photoelectrochemical properties were studied based on photocurrent measurement and impedance analysis in a three-electrode wet cell. The photocurrent was found to increase with the donor density, both in anatase and rutile electrodes. For the same donor density, however, rutile electrodes exhibited higher photocurrents than anatase electrodes, which was ascribed to the more beneficial bandgap structure of the former.