To prepare shape-stabilized phase change material (SS-PCM), polymerized high internal phase emulsion (PolyHIPE) was used as the support material, and the hexadecanol was immersed through the vacuum impregnation method. Structure and thermal properties of prepared SS-PCM were characterized by mercury injection test, scanning electron microscopy, differential scanning calorimetry analysis, thermogravimetric analysis and thermal cycling test. The pore properties of PolyHIPE can be adjusted by internal phase ratio, surfactant content and crosslinking agent content of HIPEs. Experimental parameters for PolyHIPE preparation were optimized in term of phase change enthalpy and shape stability of resultant SS-PCM. Under optimal condition, the obtained SS-PCM possess high impregnation ratio (92.6%), high phase change enthalpy (210.4 J center dot g(-1)) and excellent long-term shape stability (2.53% leakage after 1000 thermal cycles). It is highly feasible to use polyHIPE as a support material to prepare SS-PCMs, and the SS-PCMs have good energy storage capability, showing brilliant prospects in the field of thermal storage and temperature regulation.