Polyvinyl chloride ‘PVC’/(1-x)ZnMn2O4/xPbS (with and without multiwalled carbon nanotubes, MWCNTs) polymers were formed using solid state reactions and co-precipitation procedures. Rietveld analysis was applied to investigate the structure and microstructure properties of (1-x)ZnMn2O4/xPbS fillers. TEM image of the filler displayed a homogenous particle morphology with particle size 10–50 nm. The influence of nanofiller on the optical absorbance, transmittance, reflectance, refractive index, extinction coefficient, dielectric constant, and energy loss functions data of PVC polymer, with and without addition of MWCNTs, was explored. In general, the absorbance of doped PVC enhanced, and transmittance dropped. The direct/indirect optical bandgap energies Eg of PVC (4.3 and 4.09 eV) reduced attaining the lowest values (3.6 and 2.32 eV) upon loading with x = 0.1 nanofiller/MWCNTs. Also, the emitted fluorescence spectra (FL) greatly reduced; pristine PVC emitted a blue color while doped PVC emitted a blue-orange color. The effect of frequency and fillers on the dielectric constant, electric moduli, ac conductivity and energy density of all polymers was studied.