Applying solar energy over a wider spectral range can lead to more efficient energy conversion. The combination of a photovoltaic (PV) cell and a thermoelectric generator (TEG) is a widely studied technology for effectively broadening the use of the solar spectrum. In this paper, we select two kinds of photovoltaic cells and combine them with a TEG to form different systems, and analyze the overall performance of each system to provide a certain reference for optimal use of photovoltaic cells and a TEG in a hybrid system. Furthermore, we use machine learning to optimize the structural parameters of the hybrid system, and predict the optimal output power of the system when the area ratio of the TEG and PV module is 4.41. This work provides an important reference for further research on the PV-TEG hybrid system and its applications.