Graphene nanosheets offer intriguing electronic, thermal, and mechanical properties and are expected to find a variety of applications in high-performance nanocomposite materials. Dispersal of graphene nanosheets in polymer hosts and precise interface control are challenging due to their strong interlayer cohesive energy and surface inertia. Here, an efficient strategy is presented for growing polymers directly from the surface of reduced graphene oxide (GO). This method involves the covalent attachment of Br-containing initiating groups onto the surface of hydrazine hydrate reduced GO via a diazonium addition and the succeeding linking of poly(tert-butyl methacrylate) (PtBMA) chains (71.7 wt % grafting efficiency) via surface-initiated single-electron-transfer living radical polymerization SET-LRP) to graphene nanosheets. The resulting materials were characterized by using a range of testing techniques and it was proved that polymer chains were successfully introduced to the surface of exfoliated graphene sheets. After grafting with PtBMA, the modified graphene sheets still maintained the separated single layers, and the dispersibility was improved significantly. The method is believed to offer possibilities for optimizing the processing properties and interface structure of graphene-polymer nanocomposites. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4977-4986, 2011