In this study, a novel high-efficient energy-saving vacuum BIPV (building integrated photovoltaic) curtain wall, which combines photovoltaic curtain wall and vacuum glazing technologies, was developed and investigated. This vacuum BIPV curtain wall can not only perform on-site power generation, but also significantly reduce the heat transfer through the building envelope with improved thermal insulation. The thermal and power performance of the vacuum PV glazing were investigated by experiments and numerical simulations. A prototype of the vacuum BIPV curtain wall was set up for a short-term outdoor testing to consolidate its thermal and power performance under typical weather conditions of Hong Kong. A comprehensive energy model was then developed to predict the dynamic power and thermal performance of the vacuum BIPV curtain wall to evaluate its annual energy saving potential compared to other advanced window technologies used in buildings in Hong Kong. Based on the simulation model, an optimum design of the vacuum BIPV curtain wall was proposed. In addition, the annual energy-saving potential for a typical high-rise commercial building with the application of miscellaneous BIPV products was estimated using the typical meteorological data. BIPV characteristics were jointly optimized with other passive architectural design parameters and the net building energy demand can be decreased by up to 60% compared with a benchmark office building in Hong Kong. The target of near-zero energy high-rise building can therefore be further approached by this integrated design optimization process.