In this work, we synthesized poly(methyl methacrylate) (PMMA)/expanded graphite (EG) nanocomposites 6y a new polymerization method. The volume electrical conductivity of the nanocomposite prepared by this way is very high (when the content of EG is about 8 wt %, the conductivity could reach 60 S/cm). The structure of the nanocomposite was investigated by SEM, TEM, IR, and XRD. And we found temperature and voltage were important parameters of governing the electrical conductivity of PMMA/EG nanocomposites.