Undoped and doped polyvinylpyrrolidone/carboxy-methyl cellulose/zinc sulfide/nickel oxide (PVP/CMC/ZnS/NiO) nanocomposite blends with multi-walled carbon nanotubes (MWCNTs) were prepared using sol-gel and solid-state reactions and casting techniques. Various blends were formed and their composition and morphologies were characterized using X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. The structures of the nano-fillers were examined using the XRD technique. The influence of the concentrations of MWCNTs on the linear and nonlinear optical parameters of PVP/CMC/ZnS/NiO nanocomposite blends was examined. The optical band gap energies were decreased from (direct, indirect: 5.31, 5.06) eV for undoped blends to 4.38 and 3.34 eV for the blends doped with the highest concentration of MWCNTs (0.15 wt%). The refractive indices of the various blends were calculated based on the obtained optical band gap energies using various models. The effect of MWCNTs concentrations on the dielectric constants, energy density, electric modulus and ac conductivity at room temperature of the PVP/CMC/0.5ZnS-0.5NiO/x wt% MWCNTs samples were explored using an Inductance, L, Capacitance, C, and Resistance, R (LCR) meter bridge.