Aim to expand the functions of traditional building envelope windows and improve its thermal performance, a novel hybrid multi-layer CdTe based PV ventilated window system integrated with phase change material (abbreviated as CdTe-PCMVW) was proposed, constructed and experimentally investigated in this current work. Detailed fabrication process of the key component, the hybrid PV glass module integrated PCM (abbreviated as PCMG) was provided. Functions of electrical power generation, indoor passive space heating, heat preservation and ventilation cooling are integrated for this novel system, which can be realized by switching the operating modes. Different operating modes were established according to the ambient conditions and indoor thermal demands. Experiment platform was constructed and the PCMVW system was installed on it for experimental test. Two groups of continuous full-day experiments were conducted under the heating and non-heating season days. Main conclusions of the current study are: (1) Daily total electricity generation and average electrical efficiency were respectively 0.419 kWh, 0.423 kWh and 7.42 %, 7.40 % for the heating season days and 0.156 kWh, 0.159 kWh and 6.20 %, 6.33 % for the non-heating season days. (2) Utilization of PCM has realized thermal management of the PV glass, with the decrease and delay of peak temperature of PV glass. Thermal comfort rates (TCR) of the experimental room and reference room were respectively 25.51 %, 6.25 % and 37.45 %, 17.74 % for the two groups of experiment. (3) Effective lighting rates (ELR) of the novel system during the working time under the two groups of experiment were respectively 99.91 % and 98.52 %. The indoor daylighting performance of the PCMVW system was able to meet the demands of indoor daily work and life activities under the sunny days of both heating and non-heating season.