<p>This study aims to develop poly(methyl methacrylate) (PMMA)/LiTFSI (lithium bis(trifluoromethanesulfonyl)imide)/ZnW_1-xIn_xO₄ for use in a diversity of optoelectronic and radiation shielding objectives. The effect of the fillers on the structure and morphology of the host PMMA sample was assessed. The loaded samples exhibited blue–violet colors but with diverse levels. The linear attenuation coefficient (LAC) and mass attenuation coefficient (MAC) values were increased as the host polymer was loaded with LiTFSI and/or ZnW_1-xIn_xO₄ (<i>x</i> = 0, 0.05, 0.1) but they reduced as the photon energy decreased. The addition of LiTFSI and/or ZnW_1-xIn_xO₄ (<i>x</i> = 0, 0.05, 0.1) to PMMA led to a decrease in its half-value layer (HVL) and mean free path (MFP) values over the energy spectrum of (0.015–15) MeV. In loaded polymers containing LiTFSI and/or ZnW_1-xIn_xO₄ (<i>x</i> = 0, 0.05, 0.1), the effective atomic number (<i>Z</i>_eff) increased as compared with PMMA alone. An elevated fast neutron removal cross-sectional (FNRCS) value in the loaded sample with LiTFSI/ZnWO₄ compared to the other samples was observed. The impact of fillers on the buildup factors was explored. The insertion of LiTFSI and ZnW_1-xIn_xO₄ into the PMMA matrix resulted in a reduction of both exposure buildup factor (EBF) and energy absorption buildup factor (EABF) values compared to pure PMMA.</p>