Poly(vinylidene fluoride) (PVDF) is a typical semicrystalline polymer with good processing ability and exciting properties, including superior piezoelectric and pyroelectric properties. It has many applications ranging from supercapacitors, transducers, actuators to batteries. Due to the fact that the PVDF-based electronic devices become slimmer and more integrated today, improving the thermal conductivity of PVDF-based material becomes very significant today. In the present work, carbon nanotubes (CNTs) and graphene oxide (GO) were simultaneously introduced into PVDF to prepare the PVDF/CNT@GO composites. The thermal conductivity measurements showed that only addition of GO did not apparently enhance the thermal conductivity of the PVDF/GO composites. Compared with the slightly enhanced thermal conductivity of the PVDF/CNT composites with increasing CNT content, largely enhanced thermal conductivity was achieved for the PVDF/CNT@GO composites. Research on the crystallization behaviors showed that the presence of CNT@GO induced the formation of a few amount of γ-from crystal. Furthermore, morphological characterization and rheological measurements demonstrated that GO greatly improved the dispersion of CNTs and induced denser CNT network structure in PVDF matrix. The denser CNT network structure and the formation of polar crystal were suggested the main mechanisms for the largely enhanced thermal conductivity of the PVDF/CNT@GO composites.