One of the key methods to improve the energy saving performance of a building is to apply advanced materials or components to the building envelope. However, the two parts of a building's envelope, the transparent one and the non-transparent one, are usually investigated individually by existing literature. In this study, vanadium dioxide (VO2) glazing, an advanced energy-efficient element applied to the transparent parts of the building envelope, and phase change material (PCM), a typical thermal storage material used to improve the non-transparent parts of the building envelope, were adopted simultaneously for the first time. The synergetic performance of VO2 glazing and PCM, demonstrated in a full-scale, lightweight, passive room, resulted in a significant improvement in the thermal comfort degree. The Energy Saving Index (ESI) is a simple and effective indicator that can be used to evaluate the passive application performance of a single energy-efficient material or component on a common standpoint. In this work, the index was broadened to evaluate the performance of more than one material, showing that ESI is feasible and favorable to analyze the coefficient application of several building materials and/or components. Using the ESI, the performance of the synergetic application was also compared with those of the sole materials, indicating that the synergetic application has a better performance during the cooling period. Furthermore the synergetic application involves an interplay rather than a simple combination of the energy-efficient materials. The application to a heavyweight building is further discussed on the basis of performance simulations, including an economic estimation and application during the heating period. (C) 2014 Elsevier Ltd. All rights reserved.