The solution casting technique is utilized to fabricate blank and CuO-doped polyvinyl alcohol/chitosan (PVA/CS) blends for eco-friendly applications. The structure and surface morphologies of prepared samples were explored by Fourier transform infrared (FT-IR) spectrophotometry and scanning electron microscopy (SEM), respectively. FT-IR analysis reveals the incorporation of CuO particles within the PVA/CS structure. SEM analysis exposes the well-dispersion of CuO particles in the host medium. The linear/nonlinear optical characteristics were found on the basis of UV-visible-NIR measurements. The transmittance of the PVA/CS decreases upon CuO increasing to 20.0 wt%. The optical bandgap (Eg dir./Eg ind.) decreases from 5.38/4.67 eV (blank PVA/CS) to 3.72/3.12 eV (20.0 wt% CuO-PVA/CS). An obvious improvement in the optical constants of the PVA/CS blend is achieved by CuO doping. The Wemple-DiDomenico (WDD) and Sellmeier oscillator models were utilized to examine the CuO role dispersion behavior of the PVA/CS blend. The optical analysis shows clear enrichment of the optical parameters of the PVA/CS host. The novel findings in the current study nominate CuO-doped PVA/CS films for applications in linear/nonlinear optical devices.