In this paper, graphite/polystyrene nanocomposite is synthesized by in situ polymerization of styrene in a tetrahydrofuran (THF) solution system of potassium (K)-THF-graphite intercalation compound (GIC). K-THF-GIC has proved to initiate polymerization of styrene by the anionic mechanism. Due to the interfacial interaction between the graphite nanolayers and the polymer, the composites exhibit higher glass transition temperature and higher thermal stability when compared to polystyrene. The percolation threshold in the conductivity of the composites is lesser than 8.2 wt% and the dielectric constant can reach as high as 136.