The antipolar crystal form of poly(vinylidene fluoride) can be made piezoelectric and pyroelecric by the temporary application of electric fields in excess of 1 MV/cm at room temperature. Infrared and x‐ray diffraction data reveal that the polarization occurs in two stages. At fields near 1 MV/cm, a phase transition to a polar form II occurs with presumably no change in chain conformation. Fields near 5 MV/cm cause a change in conformation to produce form I. Our results indicate that at least a portion of the residual polarization occurs within the crystal phase of the polymer.