Two novel core-shell pentablock copolymer/silica hybrids are prepared for coating applications via growing silica on the precursor of pentablock copolymer PDMS-b-(PMMA-b-PMPS)(2) (PDMM), which is synthesized by dimethylsiloxane (DMS), methylmethacrylate (MMA) and 3-(trimethyoxysilyl)propyl methacrylate (MPS). The hybrid of PDMM core/silica shell (PDMM@SiO2) is obtained by the assembled PDMM in THF/CH3OH solution with tetraethyl orthosilicate (TEOS), but the hybrid of silica core/PDMM shell (SiO2@PDMM) is obtained by the hydrolyzed TEOS with -Si(OCH3)(3) groups during assembling of PDMM in THF solution. PDMM@SiO2 could produce a film distributed agminated SiO2 particles with 45 nm roughness, but SiO2@PDMM could produce a film scatted individual SiO2 particles with 26 nm roughness. Therefore, PDMM@SiO2 film gives an obvious hydrophobicity (116 degrees), higher T-g (121 degrees C), high T-d (>400 degrees C), low amount of water absorption (300 Hz of Delta f), low viscoelasticity (-0.32 of Delta D/Delta f), but tight layer structure (10 x 10(-6) of Delta D) and high storage modulus (2350 MPa). However, both core-shell hybrids have the similar adhesion to the substrate (185-187 N). (C) 2014 Elsevier B.V. All rights reserved.