[en] Electron paramagnetic resonance (EPR) and photoacoustic spectral (PAS) studies were conducted on pure polyvinyl alcohol (PVA) film, ²³⁸U(VI) doped PVA film after gamma irradiation and ²³⁹Pu(IV) doped PVA film after in-situ alpha irradiation. Studies on gamma irradiated U(VI) doped PVA film revealed the formation of U(V) complex and free radical -CH₂-C(OH)CH₂-. The later was also formed in pure PVA film. The in-situ alpha-irradiation resulted in a broad line at g=1.998±0.001 in addition to weak lines due to -C(O)=CH₂- and -CH₂C(OH)CH₂-. The broad line appears to be due to high local concentration of these radicals which increased with longer in-situ irradiation. With long storage, a doublet, presumably due to interaction of -C(O)=CH₂- with I=1/2 of ²³⁹Pu got evolved. (author)