Polymer gels and films, due to their near equivalence to biological tissue, are amongst the most promising future dosimetry tools for medical applications. The application of polymer dose gels is limited by the sensitivity of dose readout methods and dose gel properties. It is a challenge to find suitable dosimeters for registration of doses delivered to the target by orthovoltage therapy units. The application of metal-particle-enriched polymer composites for dose registration in X-ray therapy might be an elegant solution, especially if recent dose-reading technologies exploring advantages of different physical phenomena are involved. In this work, X-rays from the orthovoltage therapy range were used for the irradiation of experimental samples. In addition, radiation-induced processes of formation of silver nanoparticles in AgNO3–PVA gels and in free standing AgNO3PVA films, also containing some additional solvents, namely glycerol, ethanol, and isopropanol, have been investigated, with the aim to apply the developed composites for medical dosimetry purposes. A simple and environmentally friendly method for the formation of free-standing AgPVA films at room temperature was proposed and realized for preparing AgPVA films for investigation. Radiation-induced synthesis of silver nanoparticles in AgPVA composites was investigated, analyzing LPSR-based UV-VIS spectral changes to the irradiated films with respect to irradiation doses, and dose-related tendencies were also evaluated. It was shown that AgPVA films were more sensitive for detection of doses from the interval 0–1.0 Gy, thus indicating potential application of AgPVA films for dosimetry purposes.