Developing different types of radiation shielding with certain specifications according to the type of radiation and method of application is essential. In this work, the radiation shielding, optical and structural features of PVA films containing BaTiO3 nanoparticles are investigated. The radiation shielding properties were measured experimentally with real gamma sources (133Ba, 152Eu, and 137Cs). The efficiency calibration and spectrum analysis were performed with the Spectra Line Ultimate Gamma Lab packet program. Moreover, the results were compared with the FLUKA Monte Carlo code. Before radiation attenuation measurements, the prepared films were characterized via X-ray diffraction (XRD). The structure of the BaTiO3 nanoparticles in the polymer matrix was studied with a scanning electron microscope (SEM, Merlin, Carl-Zeiss, LEO982). In addition, the optical properties of the polymer films were studied and presented. As the BaTiO3 content increases in the polymer matrix, transmission decreases and reflectance increases. Equally, as the BaTiO3 content increases, the value of α increases. For the shielding properties, the mass attenuation coefficient (μm) increases as the BaTiO3 content increases from 0.65 to 3.57 wt%. There is a strong agreement between experimental results and the values obtained from the FLUKA Monte Carlo code.