Poly(ethylene terephthalate) (PET) is able to retain space charge in traps, as is usual in dielectric materials. This allows the material to attain an almost permanent polarization when space charge is displaced by an external electric field or is injected from an electrode. We have studied the influence of UV irradiation on the charge trapping capability of PET in samples exposed for different periods of time, up to 10 weeks. The pulsed electro-acoustic technique (PEA) has been used to determine the charge profile. The injected charge that the material is able to retain on the irradiated surface increases with irradiation time. This indicates the formation of new traps. An extensive characterization of these localized states has been performed by the technique of thermally stimulated depolarization currents. Parameters of charge relaxation kinetics have been obtained by fitting spectra of the space charge relaxation current of a semicrystalline polymeric material peak (), related to injected charge, to the general-order kinetics model. A relaxation map analysis shows that relaxation times become more distributed and the activation energy decreases as irradiation time is increased. The activation energy decreases by approximately 10% after 10 weeks of exposure. These results show that UV irradiation creates additional traps on the treated surface, which agrees with PEA results, and that the energy depth of these traps is shallower and it is more distributed than in the case of pre-existing traps.