The &agr;‐ phase chain of poly(vinylidene fluoride) has a component of dipole moment parallel to the chain axis which can be reversed by propagation of a solitary wave along the chain. Calculations of the energy required to create such a wave in a perfect chain yield larger values than are implied by experiment. This suggests that either head‐to‐tail defects or regions of stress at the lamellar boundary might play an important role in causing the observed dielectric behavior.