Photovoltaic modules during sunny days can reach temperatures 35 °C above the ambient temperature, which strongly influences their performance and electrical efficiency as power losses can be up to −0.65%/°C. To minimize and control the PV panel temperature, the scientific community has proposed different strategies and innovative approaches, one of them through passive cooling with phase change materials (PCM). However, further investigation, including the effects of geometric shape, insulation, phase change temperature, ambient temperature, and solar radiation on the PV module power output and efficiency, needs further optimization and research. Therefore, the current work aims to investigate several system configurations and different PCMs (RT42, RT31, and RT25) and compare the system with and without insulation through computational fluid dynamic (CFD) tools. The final goal is to optimise and control the temperature of PV modules and evaluate their system efficiency and energy generation. The results showed that compared with a rectangular shape of the PCM container, the trapezoid-one exhibits a considerably better cooling performance with a negligible variation of the PV temperature, even when the melting temperature of the PCM was lower than the average ambient temperature. Moreover, the study showed that having insulation in the PCM container increases the amount of PCM needed, compared with no insulation case, and the increased amount depends on the PCM type. The newly proposed PV/PCM system configuration shows an efficiency and power generation enhancement of 17% and 14.6%, respectively, at peak times.