The poly (arylene ether nitrile) s containing phthalazinone moiety end-capped by hydroxyl group (PPEN-OH) were successfully synthesized by the nucelophilic displacement reaction of the bisphenol-like monomer, 4-(4 -hydroxyphenyl) -phthlazin-1 (2H) -one (DHPZ) and 2,6 -difluorobenzonitrile (DFBN) using tetramethylene sulfone as solvents and K2CO3 as catalyst at 190 degrees C with stirring for 5 h. Then the reaction of PPEN-OH and allyl bromide in the presence of tetramethylene sulfone as solvent was carried out,following the hydrosilylation of methyltrimethoxysilane with the solvents of tetrachloroethane and the catalyst of 4 angstrom-Pt at 105 degrees C with stirring for 23 h to get trimethoxysilane endcapped PPEN (PPEN-Si). Then the fluorine silicone hybrid material (PPEN-b-FPSO) was prepared from triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane, PPEN-Si and diphenylsilanediol using N-methyl-pyrrolidone as solvents and barium-hydroxide monohydrate as catalyst at room temperature with stirring for 36 h. The effects of reaction temperature and reaction time on the yield of target product were investigated. The structures of copolymers obtained were confirmed by FTIR, H-1-NMR and F-19-NMR, respectively. The film was fabricated from the SiO2 modified by (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane and the resulting PPEN-b-FPSO at the weight ration of 1 : 1. The thin film was dried under vacuum at the fixed temperature procedures. The surface morphology of the thin film was observed using scanning electron microscope. The film presented micro-nano rough microtextures. The contact angle of the film observed directly by DSA 100 was up to the maximum of 159 degrees. The adhesion of the film was one grade by QFZ adherometer. The results indicate that this hydrophobic coating is a prospective candidate for the application of aviation, building, environmental protection and so on.