Polystyrene (PS) graft graphite oxide (GO) was synthesized by Cu (I)-catalyzed 1, 3-dipolar cycloaddition ("click" coupling) of azido modified graphite oxide with well-defined, alkyne-terminated polystyrene. This method produced PS blocks graft on GO surface, while ordered layer structure between GO sheets was observed for the first time in GO/Polymer composite. The layered structure was characterized and confirmed by 1D X-ray diffraction (XRD) and atomic force microscopy (AFM), and the layer thickness was observed to be controlled with intercalated PS length between GO layers. (C) 2011 Elsevier Ltd. All rights reserved.