This study proposes a new method to accurately evaluate the overall building envelope thermal performance considering the window–wall correlation, providing a new tool for building thermal design. Firstly, a non-stationary room heat transfer model is established based on the Resistance-Capacity Network method. The influence of solar heat gain through the windows on the heat transfer process of the walls in the actual environment is considered, and the room’s integrated thermal resistance and integrated heat capacity indexes describing the overall room thermal resilience performance are proposed. Then, a field research test is conducted around Lhasa to obtain the local dwelling information, climate conditions, and indoor thermal environment. Numerical simulations using EnergyPlus are made to verify the effectiveness of the indexes in describing the overall building (maximum difference within 3.67% MBE and 2.92% CVRMSE) based on the field test results. Finally, the proposed envelope thermal performance index is used to analyze the local residential buildings around Lhasa. The results show that the lack of consideration of window–wall correlation has led to the failure of a local newly built building’s actual envelope performance to meet the design requirements. These findings could help to develop the thermal design method of the building envelope.