Polydimethylsiloxanes, side functionalized in different degrees with chloromethyl groups, were reacted with 4,4'-bipyridyl and crosslinking occurred by the formation of ionic (bipyridinium) groups The reactions were carried out in a silica sol-gel system, and thus, two networks were generated simultaneously amphiphile siloxane-organic and silica networks The samples, processed as films, were characterized by Fourier transform infrared spectroscopy to verify the occurrence of the crosslinking reactions Different techniques were also used to evaluate the properties differential scanning calorimetry for emphasizing the transitions, scanning electron microscopy, and atomic force microscopy for the evaluation of the morphology and surface topography The modification of the film surface topography, which depends on the solvent polarity, was also emphasized The sorption capacities of the water vapors and of liquid solvents (water and chloroform) were investigated, and the obtained values proved to be a function of the polar group's content POLYM ENG SCI, 51 78-86, 2011 (C) 2010 Society of Plastics Engineers