The crystallization behavior and crystalline structure of poly(vinylidene fluororide) (PVDF) in the presence of graphene oxide (GO) platelets were investigated using time-resolved Fourier transformation infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), as well as differential scanning calorimetry (DSC). It is shown that GO platelets induce the formation of γ phase when crystallizing from solution, but only α phase forms from melt crystallization. The crystallization kinetics of α phase is promoted due to heterogeneous nucleation ability of GO, which is probably originated from a weak π-dipole interaction between GO and PVDF. Intriguingly, after introduction of strong ion-dipole interactions between GO and PVDF by addition of an ionic surfactant (cetyltrimethylammonium bromide, CTAB), a significant amount of γ crystals are obtained during isothermal melt crystallization. Time-resolved FTIR results further provide a detailed evolution of the γ phase formation, and there are two distinct stages during the melt crystallization in the PVDF/GO composites in the presence of CTAB, i.e., a simultaneous growth of γ and α phases in the first stage, and a solid α to γ transition in the second stage. These results may provide a facile routine to manipulate the crystalline structure in PVDF/GO composites, and thus to gain desirable properties.