A series of low surface free energy silane-functional polybenzoxazine films were prepared from alkylphenol, paraformaldehyde, and 3-aminopropyltrimethoxysilane (3-APTMOS) using a facile one-step thermal curing method. The chemical structures of these benzoxazine monomers were confirmed by FTIR and H-1 NMR. The surface properties of the series of polybenzoxazine films were proved through contact angle measurement, and the lowest surface energy of these films was 14.91 mJ/m(2). Moreover, the hydrogen bond network of the polybenzoxazine systems was studied using the FTIR spectra. The result showed that the intramolecular hydrogen bonding transformed into intermolecular hydrogen bonding with increasing curing time. Based on these findings, the transformation mechanism between the intermolecular and intramolecular hydrogen bonding during the progress of curing was proposed. The thermogravimetric analysis (TGA) results indicated that the silane-functional polybenzoxazine, with a high char yield of 57.01%, possessed excellent thermal stability.