We propose a robust route to prepare supercooling microstructured phase change materials (PCMs) suitable for long-term heat storage or thermal protection applications. The new preparation method is based on polymerization of high internal phase emulsion (HIPE). Two promising polyols, erythritol and xylitol, are successfully prepared as new type microencapsulated PCM-polystyrene composites with PCM mass fractions of 62w-% and 67 w-%, respectively, and average void diameter of ~50 µm. Thermal properties of polyol-polystyrene composites and bulk polyols are studied thoroughly with differential scanning calorimetry (DSC). Microscale engineering has a significant impact on the thermal properties of polyols. Crystallization of the microscale erythritol is accelerated as compared to the crystallization of bulk PCM due to high fraction of solid surfaces in the polymer-polyol composites. Furthermore, crystallization properties of the microstructured erythritol are preserved similar in the cycling experiments. Crystallization of the bulk erythritol is found to strongly depend on the cooling rate, thermal history of the sample and surface roughness of the crucible, whereas these factors have only little impact on the crystallization of microstructured erythritol. In addition, microstructured polyolpolystyrene composites show anomalous enhancement in the specific heat as compared to bulk polyols. This enhancement may be originated from the strong polyol-surfactant interactions occurring in the composites.