A novel fluorinated silane-functional benzoxazine monomer is synthesized, and the structure is characterized by FTIR and (1)H NMR Chemical bonds Si-O-Si linkage between the benzoxazine monomer and the substrate are identified through the variation of water contact angles. The low surface free energy calculation and mechanism of the benzoxazine polymer films are proved through contact angle measurement and FTIR. The film formation property and thermal stability of the polybenzoxazine are also investigated. These results clearly show that this novel polybenzoxazine can not only bond to the substrate but also possess even lower surface free energy which is 15.5 mJ/m(2). The polymer also possesses well thermal stability with a glass transition temperature of 188 degrees C and the 5% weight loss temperatures of 276 degrees C.