An effective technique of using click coupled graphene to obtain high-performance polymer nanocomposites is presented. Poly(e-caprolactone) (PCL)-click coupled graphene sheet (GS) reinforcing fillers are synthesized by the covalent functionalization of graphene oxide with PCL, and subsequently the PCL-GS as a reinforcing filler was incorporated into a shape memory polyurethane matrix by solution casting. The PCL-click coupled GS has shown excellent interaction with the polyurethane matrix, and as a consequence, the mechanical properties, thermal stability, thermal conductivity, and thermo-responsive shape memory properties of the resulting nanocomposite films could be enhanced remarkably. In particular, for polyurethane nanocomposites incorporated with 2% PCL-GS, the breaking stress, Young's modulus, elongation-at-break, and thermal stability have been improved by 109%, 158%, 28%, and 71 degrees C, respectively. This click coupling protocol offers the possibility to fully combine the extraordinary performance of GSs with the properties of polyurethane. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013