In order to prepare black silicon material with excellent optical absorption performance for solar cell application, a micro/nano bilayer-structure is formed on the surface of textured silicon wafer by a silver assisted chemical etching method. It is found that the deeper nanoholes could form as the etching time is longer, and the surface reflectivity is reduced obviously due to the increased time of photon reflection from the nanowires. The incident light reflectivity of the prepared black silicon is significantly reduced to 2.3%, showing obviously better optical reflectance characteristics than general monocrystalline silicon wafer, especially in a wavelength range of 300-830 nm. Considering the fact that a large number of carrier recombination centers is introduced into the nanostructured crystal silicon surface, BiFeO3/ITO composite film is coated on the surface of the black silicon solar cell by magnetron sputtering process to optimize the surface defect states and improve the cell performance. The experimental results show that the lengths of the nanowires are predominantly in a range of 180-320 nm for the prepared black silicon with micro/nano double-layer structure. The reflectivity of the incident light is below 5% in a wavelength range from 300 nm to 1000 nm, and reaches a maximal value at about 700 nm. The reflectance increases slightly as BiFeO3/ITO composite film is coated on the surface of black silicon solar cell, but it is still much lower than that of general monocrystalline silicon solar cell. The open circuit voltage and short circuit current density of the black silicon solar cell increase respectively from 0.61 V to 0.68 V and from 28.42 mA/cm2 to 34.57 mA/cm2 after it has been coated with BiFeO3/ITO composite film, and the photoelectric conversion efficiency of the cell increases from 13.3% to 16.8% accordingly. The improvement in performance of black silicon solar cell is mainly due to the promotion of effective separation of photogenerated carriers, thereby enhancing the spectral response of black silicon solar cell in the whole wavelength range. This indicates that the spontaneously polarized BiFeO3 film can play a better role in improving the surface properties of black silicon solar cell. On the other hand, for the BiFeO3 film deposited on the surface of black silicon, a spontaneous polarization positive electric field could be produced, pointing from the film surface to the inside of the solar cell. This polarization electric field could also act as part of built-in electric field to contribute the photoelectric transformation of the black silicon solar cell, leading to the open circuit voltage of cell increasing from 0.61 V to 0.68 V.