In this study, a simple method to obtain pure β-phase directly from the melt process is proposed. A series of PVDF and ionic liquid (IL) was prepared by a solvent casting method with appropriate associated with the subsequent annealing treatment. IL plays a role of filler, which can create strong electrostatic interaction with PVDF matrix and directly induce β-phase crystallization on the PVDF during the melt. PVDF film sample is immersed in hot water for annealing treatment at different temperatures (25 °C to 70 °C). We found that annealing in high temperatures especially can not only increase more IL inserted into the amorphous region of polymer matrix to make more phase transformation, but also accelerate IL removal. Characteristics and performance of the PVDF films were investigated by use of FTIR, XRD, SEM, and AFM. Piezoelectric coefficient d33 as well as d31, degree of crystallinity, and sensitivity are measured in experiment to verify the performance of PVDF film.