An energy-efficient PV-PCM (Photovoltaic-Phase change material) window is proposed in this study. During the day, a portion of the incident solar radiation is converted into electricity, while excessive heat from internal sources and solar radiation is stored within the PCM infill. At night, the stored heat can be released from the PCM. Unlike existing PV windows with PCM infill, the PCM is sealed in separate modules, allowing for easy adjustment or removal to better adapt to different weather conditions. In this study, the light, thermal and electrical performance of the PV-PCM window was tested in comparison with common clear glazing window, PV window and PCM-infill window under hot summer and warm winter climate.The experiment results demonstrated the ability of PV-PCM window in delaying and reducing the peak indoor temperature in hot summer. Compared with common clear glazing window, the peak temperature reduced by 8.67, 5.35 and 10.70 °C in the three days. Correspondingly, the indoor heat gains were reduced by 364.97, 265.96 and 301.10 kJ. SHGC of the proposed PV-PCM window was reduced to <0.30, whereas the U-value was reduced to <2.50 W/(m2·K). Compared with the PV window, more power generation were observed by PV-PCM window because of the cooling effect brought by the PCM module nearby. Whilst balancing thermal regulation, the daily power generations of the 0.36 m2 semi-transparent CdTe PV-PCM window were 548.33, 316.55 and 58.85 kJ.