To address the limitations of conventional photovoltaic thermal systems (i.e., low thermal power, thermal exergy, and heat transfer fluid outlet temperature), this study proposes a photovoltaic thermal system with a solar thermal collector enhancer (PVT-STE), incorporating phase change materials for simultaneous electricity and thermal power generation and thermal energy storage. The system consists of a water based solar collector with a partially covered absorber plate utilizing photovoltaic cells, while each component is equipped with a thermal storage enclosure filled with phase change materials. The primary objectives of this research encompass the evaluation of the proposed system's performance and the identification of appropriate phase change materials for each component. To gain comprehensive insight into the effects of employing and selecting appropriate phase change materials, the study investigates various configurations under both hot and cold weather conditions of Shanghai, China. Water serves as the heat transfer fluid under real-world operational conditions. The numerical results indicate that, for the given conditions, optimal phase change material selection entails using higher melting temperatures (e.g., RT42) in the STE component and lower melting temperatures (e.g., RT31) in the PVT component. Employing the optimal phase change materials for each component, the system can store 3234 and 1802 kJ/m2 of thermal energy during the charging process in July and November, respectively. Moreover, the proposed system generates almost 1.8 and 2 times more thermal energy per square meter in July and November, respectively, compared to a standalone photovoltaic thermal system coupled with a phase change material.