Highly antireflective porous silicon surfaces with superhydrophobicity were obtained by means of chemical etching and fluoroalkylsilane self-assembly. The results show that wettability and reflectivity of these surfaces strongly depend on the etching method and the resultant surface morphology. All of the four resultant porous silicon surfaces by alkaline etching, acidic etching, thick Pt-assisted acidic etching, and thin Pt-assisted acidic etching can reduce reflectance, but the efficiency differs greatly. Except for the alkaline etching, the porous silicon surfaces produced by the other three etching methods can reach superhydrophobicity after fluoroalkylsilane modification. These differences are due to the different surface morphology and roughness. Moreover, the porous silicon surface produced by thin Pt-assisted acidic etching presents abundant holes and particles with diameters ranging from nanometers to submicrometers. This morphology enables the porous silicon surface to own a very low reflectance value that is averaged to be about 3% over the whole experimental photon wavelength spanning 300-800 nm.