Conventional anti-reflection (AR) thin films have been gradually replaced by Biomimetic sub-wavelength structures due to their good AR property of broadband wavelength, and are widely used in solar cell surface in order to increase the efficiency of photoelectric conversion. In this paper, various surface morphology biomimetic structures are successfully fabricated on Si substrate by polystyrene spheres lithography with two-step inductive coupling plasma (ICP) and high density plasma (HDP) etching processes. And various sub-micron array structures with 700 nm heights or above are successfully fabricated. Among them, the results show that sub-micron cone structure has the best anti-reflection performance, and the average reflectance are effectively suppressed below 1% within a spectral range from 300 to 1200 nm as well.