High polar crystalline phase could enhance the piezoelectric property for polyvinylidene fluoride (PVDF), which contains the piezoresponse due to the presence of polar β and γ crystalline phase. In this study, the electroactive PVDF films were fabricated under a static electrical filed (assigned as PVDFe). Polymorphism of PVDF films were analyzed by wide-angle X-ray diffraction(WAXD) and Fourier transform infrared spectroscopy (FTIR). These results showed that PVDFe exhibited more than 85% β phase fraction which was 10% higher than the films fabricated without static electric filed. The crystallinity investigated by differential scanning calorimetry (DSC) was enhanced by increasing the static electrical filed. The date of piezoelectric constant (d33) indicated that this process can obtain high piezoresponse PVDF films without further electrical poling. In addition, the effect of ionic surfactants was also investigated.