We have measured the total current [a sum of the thermally stimulated current (TSC) and the pyroelectric current] released as a function of temperature at a constant heating rate for numerous samples of poly(vinylidene fluoride) (PVF2) films which were poled in an electric field under a variety of conditions. An analysis of this data reveals significant changes in the TSC curves of room‐temperature–poled PVF2samples as a function of rest time after poling. The possible relaxation processes accounting for these changes are discussed. The pyroelectric response of these films has also been determined and a pyroelectric coefficient of 2.5×10−9C/cm2 °K has been obtained for room‐temperature–poled samples.