In order to understand the mechanism of optical image storage in photorefractive polyvinyl alcohol (PVA) films, photo-EPR and photoacoustic spectral investigations were carried out on PVA films doped with Cr3+ and VO2+. The EPR spectrum of Cr3+ has shown reduction in intensity onin situ illumination with copper vapor laser (CVL). The decay and recovery of Cr3+ signal, with and without CVL illumination respectively, was monitored at different temperatures in 10–300 K region. These were found to obey a double exponential, with one time constant independent of temperature, and the other showing significant temperature dependence. From Τ(T), activation energy for the charge carrier transport in one of the processes was estimated to be 0.016 eV. The PA spectra showed shift towards lower wavelength side on consecutive runs. On the other hand, VO2+ doped PVA film has not shown any significant changes in intensity on laser illumination. These observations suggest (i) interaction of PVA matrix with excited Cr3+ and (ii) predominant non-radiative relaxation in VO2+: PVA system with no change in the oxidation state.