The most efficient way to create novel materials that may be used in a variety of optoelectronic applications is thought to be doped mixed polymers with appropriate fillers. Undoped and doped PVC polymers with ZnS/Mn formed at different temperatures were fabricated using the casting method. The Rietveld method was used to discover the structure and microstructure of Zn0.95Mn0.05S prepared at T = 300, 400, and 500 °C. The distribution and existence of the nanofiller over the PVC matrix were determined via XRD, FTIR, EDS, and SEM techniques. The effect of the preparation temperatures of the ZnS/Mn nanofiller on the absorption, transmittance, reflectance, refractive index, extinction coefficient, dielectric constant, AC conductivity, electrical modulus, and DC conductivity activation energy data of the PVC polymer was studied using the diffused reflectance technique. Doping PVC with ZnS/Mn (prepared at 300 °C) lowered the direct and indirect optical band gaps from 5.4 and 4.52 eV to minimum values of 4.55 and 3.63 eV. The fluorescence intensity of pure PVC is greatly enhanced upon loading with ZnS/Mn. The PVC exhibited two near UV peaks, one violet and one blue color, while, in addition, the doped polymers exhibited green and orange colors. The corresponding CIE diagram for all the samples was also determined.