With the growing concern over global warming, increasing interest has been enhancing building energy efficiency to reduce carbon emissions. Although double skin façades (DSF) are commonly used in modern architectural design and construction, their shortcomings during summer months have become apparent, highlighting the need for further improvement. This study aims to develop a novel glass façades structure, the Double Plant-Skin Façades (DPSF), which optimizes building energy efficiency and thermal environment . A comparative analysis of two façades in Wuhan was conducted to examine differences in thermal performance systematically. The findings indicate that the employment of DPSF reduces up to 3.7 °C in indoor temperature compared to DSF, leading to a 16% decrease incooling energy consumption. The air layer and indoor temperature relief were achieved through external ventilation of the DPSF’s air layer. In addition, the cooling mechanism and heat exchange process of the DPSF are analyzed. It is observed that the microclimate created by the living wall system enhances air layer heat exchange in DSF. The living wall system not only blocks solar radiation, but also increases the thermal resistance of DSF, reducing the radiant and convective heat, while evaporation of a living wall system converts sensible heat into latent heat.