Polyhedral oligomeric silsesquioxane (PUSS) end-capped diblock copolymers are synthesized using aminopropylisobutyl PUSS (ap-POSS-Br) to initiate atom transfer radical polymerization (ATRP) of methylmethacrylate (MMA) and methacrylisobutyl POSS (MA-POSS). Their chemical structures are confirmed as ap-POSS PMMA(152.0)-b-KMA-POSS)(4.3, 4.8, 10.0) with 19,840-24,770 g mol(-1) by H-1 NMR and SEC. In tetrahydrofuran (THF) solution, the obtained diblock copolymers could self-assemble into 150-300 nm core-shell micelles as ap-POSS/MA-POSS core and PMMA shell, or 164 nm core-shell-crown micelles as P(MA-POSS) core, PMMA shell and ap-POSS crown when P(MA-POSS) content is increased. These micelles can produce typical films with lower surface roughness (0.816-1.690 nm), lower water absorption and lower viscoelasticity, but higher hydrophobicity (112-126 degrees water contact angle) and higher thermostability in glass transition temperature T-g > 110 degrees C and decompose temperature T-d > 380 degrees C than pure POSS-PMMA film. In this study, the results strongly support the potential application of the PUSS end-capped diblock copolymers as the coatings. (C) 2014 Elsevier Inc. All rights reserved.