Polyvinyl chloride (PVC) is a material that decomposes rapidly when irradiated by charged particles. Here we use energy spectra of electrons reflected from the PVC films during electron radiation to monitor this process. This is accomplished by measuring the energy distribution of elastically scattered electrons which depends on the mass of the scattering atoms. Incoming electrons with energy between 5 and 40 keV are used. Information is obtained about both the relative amount of Cl, C and H present in the sample. Especially the Cl concentration decreases quickly during irradiation. At larger energy losses the signature of the band gap is visible in the energy loss spectrum. The number of excitations within the band gap increases rapidly when the composition of the film changes. The H intensity is somewhat less affected by the electron beam than the Cl intensity but accurate determination of the H content is complicated due to the changing background. Medium-energy ion scattering measurements (using 200 keV protons) and Rutherford backscattering measurements (using 2 MeV He ions) showed a strong decrease in the measured Cl intensity with ion fluence used. The Cl concentration as a function of fluence for electrons, protons and He ions can be described in a uniform way by considering the density of electronic excitations produced under the different irradiation conditions.