Novel organic/inorganic hybrid for coating material is prepared by the pentablock copolymer PDMS-b(PMMA-b-PMPS)(2) (PMMDMM) and SiO2 nanoparticles. PMMDMM is obtained via atom transfer radical polymerization (ATRP) by using polydimethylsiloxane (PDMS) as bifunctional macroinitiator. Poly 3-(trimethoxysilyl)propyl methacrylate (PMPS) is designed as the end block for facilitating the chemical bond of triethoxysilane (-Si(OCH3)(3)) groups with SiO2 nanoparticles produced by tetraethyl orthosilicate (TEOS), and poly (methyl methacrylate) (PMMA) is designed as the middle block for improving the solubility and the film-forming ability of copolymer. The homogeneous dispersion of SiO2 nanoparticles in the pentablock copolymer matrix enables PMMDMM/SiO2 to self-assemble into 210 nm SiO2 core/PMMDMM shell elliptic or spherical micelles in tetrahydrofuran (THF) solution. This self-assembled aggregate could provide the film surface with uniform distribution of SiO2 nanoparticles, obvious hydrophobicity (101-102 degrees water contact angles), lower surface free energy (22.3-21.8 nN/m) and lower viscoelasticity. SiO2 involved into the copolymer matrix could increase the nanostructures roughness. When TEOS is controlled as 20 wt.%, the hybrid performs higher glass transition temperature (T-g = 113 degrees C) and excellent thermostability (520 degrees C) than PMMDMM (T-g = 87 degrees C, 295 degrees C) due to the introduction of SiO2 nanoparticles. These excellent properties promise PMMDMM/SiO2 hybrid as the candidate for coating material. (C) 2013 Elsevier Inc. All rights reserved.