In this study, polyaniline (PAni)/poly(vinylidene fluoride) (PVDF) blends of different compositions were prepared by in situ chemical polymerization of aniline in a mixture of PVDF and dimethylformamide (DMF). Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetry (TG) and differential scanning calorimetry (DSC) were utilized to understand the effect of different amounts of in situ PAni loading on the crystalline structure, phase transition and dynamic melt-crystallization kinetics of PVDF. The images for morphology obtained using scanning electron microscopy and polarizing optical microscopy also provided the confirming evidences. FT-IR studies revealed that the transition of the crystalline structure (from β- to α-phase) of pure PVDF during recrystallization is hindered by the incorporation of PAni within the matrix. The dynamic crystallization kinetics data were analysed with different macroscopic models to describe the polymer crystallization, and the parameters obtained from the analyses were correlated with the structural evidence to verify their applicability for the systems under investigation. Values for the effective activation energy (E_X) of the crystallization process of PVDF and its blends were calculated by the differential isoconversional methods of Friedman. It was observed that, although PAni acted as an effective nucleating agent to induce a great number of heterogeneous nuclei within the blends, it actually delayed the overall crystallization process. The increased values of the crystal growth parameters obtained from the analysis of the temperature-dependent E_X by the modified Hoffman–Lauritzen theory also support the above mentioned interpretations.