In this paper, we adopted hot-pressing treatment to convert the regular reduced graphene oxide (RGO) from chemical exfoliation to the high-quality graphene (HQG), and then the HQG/poly vinylidene fluoride (PVDF) composite films were prepared by spin coating. The microstructural characterizations and property measurements revealed that (1) The HQG was free of defects and oxygen-containing functional groups on the surface, and exhibited a homogeneous dispersion and a well composite with PVDF; (2) The storage modulus of the HQG/PVDF composite was nearly twice higher than that of RGO/PVDF composite, and eight times higher than that of pure PVDF; and (3) The optimum additive amount of HQG with PVDF was at between 3 and 5 wt%. It is expected that the present HQG has a potential applications in polymer composites.