New amphiphilic polymer networks were synthesized by the free-radical copolymerization of alpha omega-diacryl polycaprolactone (DAPCL) and N-vinylpyrrolidone (NVP), which was initiated by 0.5% azobisisobutyronitrile at 70 degrees C. The chemical structures of the networks were characterized by proton nuclear magnetic resonance spectrometry. The NVP/DAPCL feed ratio played an important role in the crosslinking process. The synthesized amphiphilic polymer networks exhibited controlled swelling properties in water and organic solvents (ethanol, acetones, and toluene). A porous structure was observed for the amphiphilic polymer networks under a scanning electron microscope. (C) 2007 Wiley Periodicals, Inc.