Thermal interface materials with high thermal conductivity are essential to transfer the redundant heat and improve the reliability of integrated circuits. Here we reported high thermal conductivity in polydimethylsiloxane (PDMS) nanocomposite incorporated with few-layer graphene, which was exfoliated in chloroform with assistance of hyperbranched polyethylene-g-polyhedral oligomeric silsesquioxane copolymer (HBPE@POSS) as the stabilizer. In order to improve the compatibility and enhance the thermal property, the HBPE@POSS copolymer was synthesized via the unique chain walking polymerization mechanism, which subsequently was applied to exfoliate natural graphite into few-layer graphene in low-boiling-point solvents. The majority of resultant nanosheets with low defects was verified with lateral dimension of ~400 nm and the thickness of ~1.6 nm, which is attributed to the presence of CH-π noncovalent interaction between graphene and HBPE@POSS copolymer. The graphene nanoplates (GNPs)/polydimethylsiloxane (PDMS) nanocomposites were prepared by solution casting, in which graphene nanofillers were dispersed uniformly in the matrix due to good compatibility between PDMS and oligomeric silsesquioxane segments adsorbed on the nanosheets. The thermal conductivity of 4.0 wt% GNPs/PDMS nanocomposite reaches 0.93 W m  K, which is 400% higher than that of pure PDMS. The PDMS nanocomposite incorporated with few-layer graphene exhibits a promising prospect in thermal interface for thermal management of electronic devices, and sheds a light on the interfacial improvement mechanism of thermal conductivity for polymer composite.