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This paper presents that polyethylene glycol (PEG) synthesizes a form-stable phase change material (FS-PCM) with high thermal conductivity and considerable heat storage density. PEG was confined to the chain structure of epoxy resin (EP) via high-temperature melt blending and curing, which solves the leakage problem of PCMs during phase transformation. In order to increase the thermal conductivity and stability of the PEG/EP while maintaining good heat storage capacity and insulation ability, a low loading of reticulated porous Al 2 O 3 ceramic (RPC) was introduced into the PEG/EP matrix. RPC increases the thermal conductivity of FS-PCM by 5.5 times and the heat storage rate by 4 times. In addition, FS-PCM filled with 13.8 vol% RPCs has a coefficient of thermal expansion (CTE) of 80 ppm/K at 85–150 °C -a decrease of 62% over the matrix. Furthermore, the BN network is formed on RPC by vacuum impregnation technology, which further improves the thermal conductivity. This novel FS-PCM has excellent comprehensive properties and does not need for case package, indicating great prospects in thermal management and thermal storage. [ABSTRACT FROM AUTHOR]