Energy consumption in the building sector has increased dramatically over the past two decades. The incorporation of phase change materials (PCMs) into building envelopes is considered as effective thermal energy storage to improve building thermal performance and reduce space heating/cooling load. Despite significant efforts in PCMs technologies and their application to buildings, how to select proper PCMs for buildings and maximize the activation of their latent heat to effectively improve building energy efficiency still post great challenges. The lack of systematic and comprehensive studies in these gaps hinders their broad applications in the building sector. This study aims to develop a holistic framework through experimental and numerical studies to gain a deep understanding of the thermal property of PCM and the heat transfer mechanism of the exterior wall integrated with PCM. A novel shape-stabilized paraffin/expanded graphite(EG) composite is prepared and its thermal behavior is investigated through thermal energy storage and heat transfer test. The impact of critical design parameters including the location, thickness, latent heat, melting point, and thermal conductivity of PCM on the thermal performance of a multilayer wall is explored using COMSOL Multiphysics® software. The thermal storage and heat transfer test show that EG can significantly enhance the heat transfer rate of paraffin. In addition, the paraffin/EG composite possesses favorable thermal energy storage ability to decrease the indoor temperature fluctuation and shift the peak load. Among the aforementioned design parameters, melting point of PCM is critical to significantly influence the building thermal performance. To effectively account for melting point of PCM and enhance the service efficiency of PCM, a new wall configuration containing PCM with hybrid melting points is proposed. The proposed wall assembly is found to benefit the indoor thermal comfort and the activation of the latent heat of PCM when the ambient temperature covers cold, mild, and hot loading conditions for the long term. Moreover, coupling vacuum insulation panels (VIP) with extremely low thermal conductivity and PCMs with a large amount of latent heat in the building envelope is another solution to further enhance building thermal performance due to the increased thermal insulation and thermal inertia.