The crystallization and melting of poly(vinylidene fluoride) as a function of hydrostatic pressure was investigated. Poly(vinylidene fluoride) can be crystallized in at least two crystalline modifications at pressures of 1 atm (phase I and phase II). The crystallization of poly(vinylidene fluoride) under hydrostatic pressure over a range of conditions yields a new crystalline phase, designated phase III. The new phase melts at 185°C, approximately 25C° higher than phase I or phase II.