Orientation of molecular dipoles in poly(vinylidene fluoride) (PVF 2) films under electric field has been measured by ir spectroscopy using ir transparent indium-tin-oxide electrodes. Significant changes in ir transmission with electric field have been observed at 512 and 446 cm -1, which demonstrate that crystalline dipoles in β-phase PVF2 orient along the electric field. As the field is cycled between positive and negative values, the dipole orientation exhibits a hysteresislike behavior, demonstrating that the polarization of β-phase PVF2 and its switching result directly from the orientation of crystalline dipoles. Time response of dipole orientation shows that the total orientation consists of an instantaneous part and a slowly developing part. Only the latter seems to contribute to the remnant polarization and its switching.