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Polyurethane (PU) is an ideal thermal insulation material due to its excellent thermal properties. The incorporation of Phase Change Materials (PCMs) capsules into Polyurethane (PU) has been shown to be effective in building envelopes. This design can significantly increase the stability of the indoor thermal environment and reduce the fluctuation of indoor air temperature. We develop a multiscale model of a PU-PCM foam composite and study the thermal conductivity of this material. Later, the design of materials can be optimized by obtaining thermal conductivity. We conduct a case study based on the performance of this optimized material to fully consider the thermal comfort of the occupants of a building envelope with the application of PU-PCMs composites in a single room. At the same time, we also predict the energy consumption of this case. All the outcomes show that this design is promising, enabling the passive design of building energy and significantly improving occupants' comfort.