PVDF is widely used piezoelectric polymer and has been extensively studied. The polarization–electric field (P-E) loops of PVDF under different electric fields have been extensively studied. However, the polarization response of PVDF under ultrahigh electric field is studied and reported here. For PVDF under 600 MV/m, a remnant polarization of 11 um/cm^2 was observed. For PVDF thick film with a thickness of 500 m, the P-E loops were obtained using ultrahigh voltage. Additionally, the abnormal peak observed in the DSC results of PVDF was explained.