We report on the rapid formation of hydrophilic silicone elastomer surfaces by ultraviolet/ozone (UVO) irradiation of poly(vinylmethyl siloxane) (PVMS) network films. Our results reveal that the PVMS network surfaces render hydrophilic upon only a short UVO exposure time (seconds to a few minutes). We also provide evidence that the brief UVO irradiation treatment does not cause dramatic changes in the surface modulus of the PVMS network. We compare the rate of formation of hydrophilic silicone elastomer surfaces made of PVMS to those of model poly(dimethyl siloxane) (PDMS) and commercial-grade PDMS (Sylgard-184). We find that relative to PVMS, 20 times longer UVO treatment times are needed to oxidize the PDMS network surfaces in order to achieve a comparable density of surface-bound hydrophilic moieties. The longer UVO treatment times for PDMS are in turn responsible for the dramatic increase in surface modulus of UVO treated PDMS, relative to PVMS. We also study the formation of self-assembled monolayers (SAMs) made of semifluorinated organosilane precursors on the PVMSUVO and PDMS-UVO network surfaces. By tuning the UVO treatment times and by utilizing mono- and tri-functional organosilanes we find that while mono-functionalized organosilanes attach directly to the substrate, SAMs of tri-functionalized organosilanes form in-plane networks on the underlying UVO-modified silicone elastomer surface, even with only short UVO exposure times. (c) 2005 Elsevier Ltd. All rights reserved.