The block copolymers of poly 2,2,3,4,4,4-hexafluorobutyl methacrylate-block-poly[3-(trimethyoxysilyl) propyl methacrylate] (PHFMA-b-PTMSPMA) were synthesized via atom transfer radical polymerization and used for the preparation of organic/inorganic hybrid materials by the sol-gel approach. The polymers were characterized by gel permeation chromatography, Fourier transform infrared and (1)H nuclear magnetic resonance. The properties of the hybrid materials were investigated by Scanning electronic microscopy, contact angle, Scotch tape test, transmittances measurement, differential scanning calorimetry, and thermogravimetric analysis. The results were as follows: First, the hybrid materials had surface roughness, good hydrophobicity (>95 degrees in contact angle with water), and could improve the contact angle of glass from 65.2 degrees to 99.9 degrees (the content of TMSPMA was 4.9 wt% in its polymer). Second, the adhesion of the hybrid materials to glass were enhanced by incorporating TMSPMA. Third, light transmittances of all the hybrid materials were above 90% in the visible range. Finally, the thermal stability of the hybrid materials were enhanced by incorporating silica moiety.