In this report, we studied the influence of silver nanoparticles (AgNPs) on the electrical conductivity of Polyvinyl Alcohol (PVA) as a semiconductor nanocomposites active layer. Here, the Schottky junction is constructed by mechanically pressing a copper (Cu) electrode onto a AgNPs-PVA nanocomposite, which shows rectification behavior at room temperature. The synthesis of silver nanoparticles (AgNPs) was achieved by the physical reduction of silver nitrate using an ultraviolet lamp. The nanocomposite films were created using a casting technique. An ultraviolet spectrophotometer (UV-Vis), which displayed maximum absorbance at 430 nm, was used to confirm the synthesis of AgNPs and carry out the optical band gap. The charge carrier transport properties of AgNPs-PVA film were investigated by using impedance spectroscopy and I–V measurements. Then, AC impedance analysis was used to determine grain and grain boundary resistances; current-voltage analysis enabled the barrier height () to be determined. Moreover, the metal/semiconductor (Cu/AgNPs-PVA) Schottky barrier was confirmed as an equivalent circuit model via the Nyquist plot. Based on thermoionic emission theory, the characteristic I–V induced rectifying Schottky behavior can be understood. Moreover, the AgNPs-PVA nanocomposite exhibited hysteresis behavior under multiple repetitive measurements. For low voltage varistor devices, the nonlinear behavior may be completely utilized.