Blended films of polyvinyl alcohol and polyethylene oxide reinforced with CuCl2.2H2O (10–50 wt%) were prepared using the solution casting technique to investigate the impact of salt concentration on structural, thermal, mechanical, and physical properties. Experimental results revealed that the thermal conductivity coefficient initially increased with rising salt content, then decreased at intermediate concentrations, and subsequently increased again at higher salt ratios. This non-linear trend suggests structural modifications due to interactions between PVA, PEO, and CuCl2.2H2O, which altered the films’ internal morphology. For mechanical properties, irregular behavior was observed in hardness, impact resistance, and tensile strength as the salt ratio increased. Fracture energy and impact toughness exhibited inconsistent trends, while elongation at break fluctuated unpredictably, reflecting changes in the films’ flexibility and structural cohesion. Physically, the true density of the films initially decreased and then increased with higher salt content. Apparent porosity first declined but later rose irregularly, whereas water absorption decreased initially before increasing steadily with salt addition. These trends indicate that CuCl2.2H2O influences polymer network formation, potentially enhancing or disrupting intermolecular bonds depending on its concentration. The study confirmed chemical interactions between PVA, PEO, and CuCl2.2H2O, which directly affected the films’ properties. The non-linear relationship between property and salt concentration highlights the need for further optimization studies to determine ideal ratios for specific practical applications.