In the relentless pursuit of sustainable energy solutions, this study pioneers an innovative approach to integrating thermoelectric generators (TEGs) and photovoltaic (PV) modules within hybrid systems. Uniquely, it employs neural networks for an exhaustive analysis of a plethora of parameters, including a diverse spectrum of semiconductor materials, cooling film coefficients, TE leg dimensions, ambient temperature, wind speed, and PV emissivity. Leveraging a rich dataset, the neural network is meticulously trained, revealing intricate interdependencies among parameters and their consequential impact on power generation and the efficiencies of TEG, PV, and integrated PV-TE systems. Notably, the hybrid system witnesses a striking 23.1% augmentation in power output, escalating from 0.26 W to 0.32 W, and a 20% ascent in efficiency, from 14.68% to 17.62%. This groundbreaking research illuminates the transformative potential of integrating TEGs and PV modules and the paramountcy of multifaceted parameter optimization. Moreover, it exemplifies the deployment of machine learning as a powerful tool for enhancing hybrid energy systems. This study, thus, stands as a beacon, heralding a new chapter in sustainable energy research and propelling further innovations in hybrid system design and optimization. Through its novel approach, it contributes indispensably to the arsenal of clean energy solutions.