The application of TiO 2 -based devices is mainly dependent on their crystalline structure, morphology, size, and exposed facets. Two kinds of TiO 2 with different structures, namely TiO 2 pompons and TiO 2 nanotubes, have been prepared by the hydrothermal method. TiO 2 with different structures is characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface area analysis. Solar cells based on poly(3-hexylthiophene) (P3HT) and TiO 2 with different structures are fabricated. In the device ITO/TiO 2 /P3HT/Au, the P3HT is designed to act as the electron donor, and TiO 2 pompons and TiO 2 nanotubes act as the electron acceptor. The effects of the TiO 2 structure on the performance of hybrid heterojunction solar cells are investigated. The device with TiO 2 pompons has an open circuit voltage (Voc) of 0.51 V, a short circuit current (Jsc) of 0.21 mA/cm 2 , and a fill factor (FF) of 28.3%. Another device with TiO 2 nanotubes has a Voc of 0.5 V, Jsc of 0.27 mA/cm 2 , and FF of 28.4%. The results indicate that the TiO 2 nanotubes with a unidimensional structure have better carrier transport and light absorption properties than TiO 2 pompons. Consequently, the solar cell based on TiO 2 nanotubes has a better performance.