A polyhedral oligomeric silsesquioxane (POSS) methacrylate monomer, i.e. 3-(3,5,7,9.11,13,15-heptacyclopentyl-pentacyclo [.9.5.1.1.(3,9)1(.5,15)1(7,13)] -octasiloxane-1-yl) propyl methacrylate (POSS-MA), was directly grafted from flat silicon wafers using surface-initiated atom transfer radical polymerization (ATRP). Two methods were used to improve the system livingness and control of polymer molecular weights. By 'adding free initiator' method, a linear relationship between the grafted poly(POSS-MA) layer thickness and monomer conversion was observed. By 'adding deactivator' method, the poly(POSS-MA) thickness increased linearly with reaction time. Poly(POSS-MA) layers up to 40 nm were obtained. The chemical compositions measured by X-ray photoelectron spectroscopy (XPS) agreed well with their theoretical values. Water contact angle measurements revealed that the grafted poly(POSS-MA) was extremely hydrophobic. The surface morphologies of the grafted polymer layers were studied by an atom force microscopy (AFM). (c) 2005 Elsevier Ltd. All rights reserved.