Novel materials that display two lower critical solution temperatures (LCSTs) were developed by forming block copolymers, laminate structures, and interpenetrating networks of crosslinked polymer systems that displayed temperature sensitivity independently. A number of LCST polymers and copolymers were investigated, including those based on N-isopropylacrylamide, N,N-diethylacrylamide, N,N-diethylaminoethyl methacrylate, and N,N-dimethylaminoethyl methacrylate. The polymer structure was found to profoundly influence the thermal sensitivity, as polymer formulation techniques led to materials with varying degrees of temperature sensitivity. Random and block copolymerization, along with interpenetrating networks and laminate systems, were studied, with only the structures having the greatest physical separation between pendent chains of different types having the ability to separate temperature transitions. Experiments were conducted to characterize the equilibrium swelling behavior and thermal transitions in the polymer systems. (C) 2003 Wiley Periodicals, Inc.