Graphite oxide (GO)/poly(methyl methacrylate) (PMMA) nanocornposites were prepared by a novel method utilizing macroazoinitiator (MAI). The MAI, which has a poly(ethylene oxide) (PEO) segment, was intercalated between the lamellae of GO to induce the inter-gallery polymerization of methyl methacrylate (MMA) and exfoliate the GO. The morphological, conductivity thermal, mechanical and rheological properties of these nanocomposites were examined and compared with those of intercalated nanocomposites prepared by polymerization with the normal radical initiator, 2.2'-azobisisobutyronitrile. The improvement in conductivity by GO was more evident in exfoliated nanocornposites compared to 10(-7) that of intercalated nanocornposites. For example, a Conductivity of 1.78 x 10(-7) S/cm was attained in the exfoliated nanocomposite prepared with 2.5 parts GO per 100 parts MMA, which Was about 50-fold higher than that of the intercalated nanocomposite. The thermal, mechanical and rheological properties also indicate that thin GO with a high aspect ratio is finely dispersed and effectively reinforced the PMMA matrix in both exfoliated and intercalated nanocornposites. (C) 2008 Elsevier Ltd. All rights reserved.