The integration of phase change material (PCM) with building-integrated photovoltaic (BIPV) presents a compelling approach to enhance solar energy utilization and mitigate indoor thermal loads, contributing to energy-efficient and low-carbon building development. Traditional BIPV-PCM structures, however, struggle to balance PV efficiency and thermal insulation, particularly with varying PCM wall positions. To address this situation, this study introduces a novel double-PCM BIPV composite envelope (BIPV-dPCM). An experimentally validated dynamic heat transfer model was developed and used to perform a comparative simulation analysis with three reference systems to quantify the energy-saving potential of the BIPV-dPCM, focusing on PV output and wall insulation effectiveness metrics. Further dimensionless parametric analysis were carried out to investigate the systematic performance of the two PCMs at different relativities. In addition, the coupled working mechanism of the BIPV-dPCM system concerning the power generation performance and thermal insulation performance under transient variations is explored. It was found that the BIPV-dPCM showcases superior thermoelectric coupling performance compared to three alternative enclosures. Incorporating two PCMs significantly enhances electrical exergy efficiency by 11.66 % and thermal exergy efficiency by 1.54 %, surpassing other reference systems. The increase in PCM latent heat ratio has a limited effect on performance gain. Notably, as the PCM thickness ratio exceeds 1, the decline in P value decelerates, for every 0.5 increment in the g, the P value diminishes by merely 0.2 %. The ideal h is identified between 1 and 1.5, with 1.5 being optimal for energy conservation objectives. Additionally, the self-sufficiency coefficient (SSC) of the BIPV-dPCM remains robust, sustaining a range of 55 % to 65 % over prolonged periods. This study offers novel perspectives and serves as a design reference for optimizing building energy systems and enhancing cooling efficiencies in subtropical climates.