Photovoltaic double-skin glass is a low-carbon energy-saving curtain wall system that uses ventilation heat exchange and airflow regulation to reduce heat gain and generate a portion of electricity. By developing a theoretical model of the ventilated photovoltaic curtain wall system and conducting numerical simulations, this study analyzes the variation patterns of the power generation efficiency of photovoltaic glass for different inclination angles, seasons, thermal ventilation spacing, and glass transmittance in the photovoltaic double-skin curtain wall system. The results indicate a positive correlation between the surface temperature of photovoltaic glass and both ground temperature and solar radiation intensity. Additionally, photovoltaic power generation efficiency is generally higher in spring and autumn than in summer and winter, with enhanced power generation performance observed. At an inclination angle of 40°, photovoltaic panels receive optimal solar radiation and, consequently, produce the maximum electricity. Furthermore, as the ventilation spacing increases, the efficiency of power generation initially rises, reaching a peak at approximately 0.4 m, where it is 0.4% greater than at a spacing of 0.012 m. For a photovoltaic glass transmittance of 40%, the highest photovoltaic power generation efficiency is 63%, while the average efficiency is 35.3%. This has significant implications for the application and promotion of photovoltaic double-skin glass curtain walls.