The objective of this study is to create nanocomposite films using polyvinyl alcohol (PVA), sodium carboxymethyl cellulose (CMC), polypyrrole (PPy) and Multi-walled carbon nanotubes (MWCNTs). These nanocomposites show potential for use in a range of optoelectronics devices. The structure and morphology of PVA/CMC/PPy/x wt % MWCNTs blends were explored using X-ray diffraction and scanning electron microscope techniques. In the visible range, the transmittance lowered from 78 to 87 % (PVA/CMC/PPy blend) to 3–5 % (x = 0.25 wt % MWCNTs). The transmittance in the UV range decreased significantly, approaching zero, for the blend containing 0.25 wt % MWCNTs. The material improves the absorption of UV–visible light and efficiently prevents the penetration of UV–visible light. When the concentration of MWCNTs reached 0.05 in the doped blend, the reflectance value improved considerably. The addition of MWCNTs to the PVA/CMC/PPy composite leads to a reduction in the optical bandgap values. The lowest direct and indirect band gaps are (4.98, 4.36) eV and (4.52, 3.19, 2.68, 1.18) eV, respectively, accomplished when the MWCNTs content was 0.2 wt %. A blend containing 0.15 wt % MWCNTs resulted in the highest values of refractive index and nonlinear optical parameters. In the visible light spectrum, the blend with 0.25 wt% MWCNTs had the best optical conductivity values. Doped blends can be used in optoelectronic or photocatalytic applications depended on the amount of MWCNTs doped. The current-voltage characteristics and logarithm of the current density and square root of the electric field strength of PVA/CMC/PPy/x wt % MWCNTs blended polymers at various temperatures were investigated.