Triboelectric nanogenerators (TENGs), a new technology for gathering sustainable energy, have attracted much scientific interest. In this study, we describe a unique method for modifying the triboelectric power generation performance of Polyvinyl Alcohol (PVA) by adding ZnO–CuO–AgO (ZCA) trimetallic nanoparticles to improve the performance of TENGs and answer the requirement for ecologically benign and biodegradable materials. Hydrothermal synthesis adopted to create ZnO–CuO–AgO trimetallic nanoparticles ensures a distinctive structure with a large surface area, essential for enhancing triboelectric power generation. From the AFM results, it is evident that 1% PVA/ZCA showed the highest output voltage of 0.27V. Despite following the general trend, at higher concentrations of ZCA nanofiller in the PVA matrix, the enhancement of output voltage is not observed, which can be attributed to the non-uniform distribution. The effect of spin-coated film thickness and nanoparticle concentration on the triboelectric performance of the PVA nanogenerator is studied by monitoring the open-circuit voltage in response to various mechanical stimuli. Finally, the developed biodegradable nanogenerators in this study can be used for sustainable energy harvesting applications such as wearable electronics, self-powered sensors, and environmental monitoring systems.