Dielectric response of vinylidene fluoride type ferroelectric polymers is dominated by that of segmental motions in the amorphous phase in temperature range 200-300 K and contributions related to the local mode and ferroelectric-paraelectric transition in the crystalline phase of the polymer at higher temperatures. Diffuse and frequency-dependent dielectric anomaly observed in fast electron irradiated polyvinylidene fluoricle-trifluoroethylene P(VDF/TrFE) has been related to relaxor-like behavior induced in the semicrystalline ferroelectric copolymers. As random field and the response of polar nanosize clusters determine the relaxor behavior the effects of disorder and fast electron irradiation (below and above T-C) on the three contributions to the dielectric response of PVDF, P(VDF/TrFE)(75/25) and P(VDF/TrFE)(50/50) are shown. The processes involved in radiation-induced functionalization of PVDF-type polymers are discussed on the basis of results of ESR, IR and Raman spectroscopy studies. (c) 2006 Springer Science + Business Media, Inc.