Most of existing solar ventilation envelope systems adopt a single structure including a glass cover a massive wall, which possesses the drawbacks of low thermal efficiency and poor stability. In recent decades, auxiliary power generation devices, led by photovoltaic (PV), have made epochal achievements in integrated building applications, while the superior thermal regulation capability of thermal storage materials, represented by phrase change materials (PCM), has further helped to improve the thermal environment of buildings, and the above two technologies have demonstrated great energy conservation potential. In order to explore the application and synergistic effect of the above two energy-conservation technologies in passive ventilation envelopes, a novel functional ventilation building envelope (FVBE) integrated with PV panel and PCM is proposed in this paper. A comprehensive exploration of the influence of various key parameters on the thermal performance of the FVBE-PV/PCM system. The electrical and thermal performance of the system is explored based on different seasonal climates. Specifically, effects of thickness as well as the melting temperature of PCM and the air channel width has been provided in this study. Taking the inner wall surface temperature (Tinner_wall), equivalent indoor load (Qload) and electrical efficiency (ηe) as evaluation indexes, the thermal efficiency, electrical performance and the coupling mechanism was assessed. Specifically, the coupling mechanism between the thermal performance and electrical performance of the FVBE-PV/PCM system was analyzed from the perspective of combined heat and power, revealing the functional characteristics of the system. Meanwhile, the article conducted a comparative study on the thermal and electrical performance of a typical building integrated PV (BIPV), FVBE-PV system FVBE-PV/PCM system. In particular, energy and exergy analysis is carried out to characterize the energy utilization of the FVBE-PV/PCM system in different structural systems. The research found that increasing the thickness of both the PCM and air channel leads to lower indoor temperature and heat flux, with different optimal phase transition temperatures for summer and winter. Although the FVBE-PV system exhibited a maximum 3.12 % reduction in power generation efficiency compared to the BIPV system due to increased PV temperature caused by air layer insulation, incorporating PCM can reduce exergy losses by an average of 31.731 % to mitigate this drawback and improve energy efficiency. Additionally, the analysis revealed varying coupling correlations between thermal performance and power generation based on two key parameters. This study could contribute to the functional improvement of the building envelope and simultaneous indoor thermal regulation.