The polymeric material polyvinyl pyrrolidine/carboxymethyl cellulose (PVP/CMC) was mixed with different quantities of tungsten-trioxide nanoparticles (WO₃ NPs). The samples were created using the casting method and Pulsed Laser Ablation (PLA). The manufactured samples were analyzed by utilizing various methods. The halo peak of the PVP/CMC was located at 19.65°, confirming its semi-crystalline nature, as shown in the XRD analysis. FT-IR spectra of pure PVP/CMC composite and PVP/CMC composite incorporated with various contents of WO₃ obtained a shift in band locations and change in intensity. Optical band gap was calculated via UV–Vis spectra, which decreased when increasing the laser-ablation time. Thermogravimetric analyses (TGA) curves showed that samples’ thermal stability had improved. The frequency-dependent composite films were used to determine AC conductivity of the generated films. When increasing the content of tungsten-trioxide nanoparticles, both (ε′) and (ε′′) increased. The incorporation of tungsten trioxide enhanced the ionic conductivity of PVP/CMC/WO₃ nano-composite to a maximum of 10⁻⁸ S/c. It is expected that these studies will have a significant impact on several utilizations, such as energy storage, polymer organic semiconductors, and polymer solar cells.