A strategy for fabricating the functionalized self-assembled films is proposed. Through the comparison of three self-assembled films of 3,4,9,10-perylene tetracarboxylic acid (PTA) with different connecting ligands, i.e. oxalic acid (Ox), succinic acid (Su), or terephthalic acid (Tp), it was found that the optimal system was composed of oxalic acid, Ce4+ and 3,4,9,10-perylene tetracarboxylic acid,which was much better than simple covalent connecting PTA films and the connecting ligands played an important role for the properties of self-assembled (SA) films. All these films were characterized by contact angle, UV spectra, cyclic voltammetry and XPS. The photocurrent generation of the best system were 5 706, 7 345 nA·cm-2, respectively, being among the highest values of dye-sensitized indium tin oxide (ITO) systems. The effects of light intensity, bias voltage, and electron donor on photoinduced electron transfer properties were also studied. The possible mechanism of electron transfer is proposed.