In this work, graphene was modified by the grafting of poly(vinylidene fluoride) (PVDF) using Friedel-Crafts reaction to form PVDF-grafted graphene (PGG) filler, which was confirmed by transmission electron microscope, Fourier transform infrared, Raman spectroscopy, wide angle X-ray diffraction, and thermo-gravimetric analysis. The solution containing as-prepared PVDF-grafted graphene and PVDF was electrospun to form fibrous membranes, which was subjected to hot pressing in the laminating mode to prepare solid PGG/PVDF composite films. The structures of electrospun fibrous membrane and solid PGG/PVDF composite film were investigated by scanning electron microscope. Furthermore, it could be found that the dielectric constants of PGG/PVDF composites exhibiting relatively low dielectric loss factors were significantly higher than that of pure PVDF.