Poly(vinylidene fluoride/trifluoroethylene) copolymers of different molar ratios in the range between 60:40 and 80:20 have been studied by thermally stimulated processes, namely thermally stimulated depolarization current, thermally stimulated current and differential scanning calorimetry, and by dielectric constant measurements. The results obtained show unequivocally that a ferroelectric-to-ferroelectric phase transition exists for 70:30 and 75:25 copolymers, in addition to the well-known ferroelectric-to-paraelectric transition, which has already been observed in all copolymers.