In order to improve the compatibility between inorganic semiconductor and organic polymer semiconductor, and optimize the photoelectric performance of the battery, a hybrid solar cell of TiO2/PCPDTBT based on one dimensional inorganic TiO2 nanorods ordered arrays and organic polymer PCPDTBT is constructed. The heterojunction interface properties between the inorganic and organic materials are controlled by amphiphilic organic triphenylamine-type molecules. The properties of the hybrid films are characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), energy dispersive spectrometer (EDS), UV-vis spectra (UV-vis), photoluminescence spectroscopy (PL), etc.. The battery performance tests demonstrate that the photovoltaic performance of the modified cell is improved, and the power conversion efficiency η is of 0.81%. Open circuit voltage decay tests demonstrate that the electron lifetime is increased after heterojunction surface/interfacial modification. These results indicate that the amelioration of morphology and structure of the active layer plays an important role on solar cell performance, by means of modification of the heterojunction surface/interface.