In order to provide multiple electron transmission channels and increase the load of narrow gap semiconductor and organic semiconductor, the array of TiO₂ dendritic structure assembled by nanotube and nanowire is constructed on FTO glass by hydrothermal method. Narrow gap semiconductor Sb₂S₃ is fabricated on dendritic TiO₂ successfully by chemical bath deposition (CBD) method. By means of SEM, XRD, UV visible absorption spectrum, transient photocurrent, steady-state fluorescence spectrum and J-V curve, the morphology, crystal shape, light absorption and photoelectric properties of the samples are characterized and tested. The effect of deposition time on power conversion efficiency (PCE) is further studied. The results show that sparse TiO₂ dendritic structure formed vertical to the FTO substrate might be a benefit for the fast electron transport; the addition of Sb₂S₃ strengthens the absorption of visible light, improves the photocurrent intensity, increases the intensity of fluorescence quenching and facilitates the generation and transfer of photogenerated carriers; the PCE of hybrid solar cell (HSC) based on dendritic TiO₂/Sb₂S₃/P3HT/PEDOT∶PSS/Au structure reaches 1.10%, and this PCE is 10 times that of the HSC without Sb₂S₃. The deposition of Sb₂S₃ on the multistage structure TiO₂ is conducive to improving the absorption of visible light, strengthening the transmission capacity of the optical carrier, broadening the spectrum response range and improving the photoelectric performance. It is of great significance to solve the problems of weak absorption intensity and narrow spectrum response range of simple TiO₂ electrodes.