The fullerene grafted poly(epsilon-caprolactone) (PCL) was successfully synthesized with a graft efficiency of 80%. The fullerene moieties grafted onto the PCL chain aggregate into 1-2 mu m particles so that a physical pseudo-network is formed. Because of the existence of the network structure, the fullerene grafted PCL film can retain its shape at much higher temperatures than that of pure PCL film, as observed in dynamic mechanical tests. It shows a hydrophobic gelling behavior in chloroform solution. (C) 2007 Wiley Periodicals, Inc.