Abstract In this work, the effect of N ‐Butylpyridinium hexafluorophosphate ([BuPy]PF 6 ) on the crystalline phase and phase transition of poly(vinylidene fluoride) (PVDF) was investigated in detail. The results show that [BuPy]PF 6 can induce the crystallization of β‐PVDF crystals from the melt. With an increase in [BuPy]PF 6 content from 0% to 20%, the content of β‐PVDF crystals rises from 16.7% to 65.6%. Taking the composites containing 4% and 20% [BuPy]PF 6 as examples, the in situ annealing process at 160 °C were tracked with the application of FT‐IR spectra. It has been confirmed that the annealing process leads to a polar phase transition from α to γ, particularly evident in samples with a 4% [BuPy]PF 6 content, where the polar phase content rises from 48.1% to 61.4%. Furthermore, the α→γ phase transition improves the piezoelectric properties of PVDF films. After annealing, the piezoelectric coefficient d 33 of samples with a 4% [BuPy]PF 6 content increases from 4.2 to 5.5 pm/V.