The synthesis of an amphiphilic polysilane with poly(ethylene oxide) grafted segments (PS-g-PEO) through the addition of an allyl-terminated poly(ethylene oxide) (AT-PEO) to poly[diphenylsilane-co-methyl(H) silane] (PSH) in a homogeneous system and using catalyst platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane is reported The process involves the activation of the polymer by microwave irradiation as a preliminary stage with the view to perform the subsequent addition stage at room temperature, when side reactions are prevented. The PS-g-PEO structure was characterized by NMR, FT-IR spectral analysis and GPC methods. The amphiphilic properties were estimated by comparison of the water sorption isotherms of the PS-g-PEO copolymer with those of the component segments. The core-shell micellization in water and the morphological aspects of the self-assembled structures were investigated by DLS and SEM. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012