Here we report a facile approach to achieve pure polar phase of poly(vinylidene fluoride) (PVDF) during melting processing of its nanocomposites containing GO, showing great potential in electroactive applications. During melt crystallization, Graphene Oxide platelets were only found to promote the crystallization kinetics of non polar α phase of PVDF, resulting primarily from the weak π-dipole interaction between GO and PVDF. Of great interest, however, was the desirable finding that nucleation of polar γ phase was substantially assisted by constructing strong ion-dipole interactions for PVDF/GO nanocomposites in the presence of an extremely low amount of cetyltrimethyl ammonium bromide (CTAB). The underlying evolution regarding the formation of γ phase, as further revealed by in-situ FTIR, gave some interesting results. Specifically, there are distinct into two stages during the melt crystallization, i.e., a simultaneous growth of γ and α phases during the first stage followed by a solid α to γ transition during the second stage. more importantly, compared to pure PVDF sample, the toughness of PVDF/GO composites containing CTAB was significantly improved without sacrificing the strength. It was presumably attributed to the high toughness of γ spherulites with a smaller size. this work emphasizes the desirable features that pure polar γ of PVDF can be achieved easily by tailoring the PVDF-GO interactions (i.e. ion-dipole interactions trough the introduction of an ionic surfactants).