Electrical conductivity of blends and composites of poly(vinyl chloride) (PVC) with nonconducting polyaniline (PANI) increases when they are subjected to gamma-rays or UV radiation. This is attributed to a radiation-induced dehydrochlorination (loss of HCl) of PVC, which in turn oxidizes (dopes) PANT within the PVC matrix causing the increase in electrical conductivity of these films. XPS, UV-vis-NIR and FTIR spectroscopic methods are used to characterize and verify this novel process. After the films are subjected to gamma-rays (or UV radiation) the intensities in the XPS spectra of both -N+- and Cl- peaks increase, confirming the increase in charged species within the PVC matrix. Similar observations attributable to radiation-induced electrical conductivity are also observed in both the UV-vis-NIR and FTIR spectra. This radiation-induced conductivity can also be reversed to some extent by further exposing the films to NH3 vapors, where the oxidized centers are partially reduced (undoped). Several UV/NH3/UV cycles can be performed without much loss in conductivity-and/or conductivity-related spectroscopic features. The onset of the photoinduced conductivity both in PVC-only and PVC/PANI composite films is determined to be 300 nm (4.1 eV), which coincides with the first UV absorption band of PVC.