Three kinds of new polymeric SSPCMs with different crosslinking structures were synthesized and characterized for thermal energy storage. In the SSPCMs, three hexahydroxy compounds (sorbitol, dipentaerythritol and inositol) were individually employed as the molecular skeleton and polyethylene glycol (PEG) was used as the phase change functional chain. The molecular structure, crystalline properties, phase change behaviors, thermal reliability and stability of the synthesized SSPCMs were investigated by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetry (TG), respectively. The results show that the prepared SSPCMs possess high thermal energy storage density and an applicable temperature range of 30-70 degrees C, and the maximum phase change enthalpy in the heating and cooling process for the SSPCMs is 107.5 kJ/kg and 102.9 kJ/kg, respectively. The prepared SSPCMs have good reusability, excellent thermal reliability and stability from the heating-cooling thermal cycle test and TG curves. The resultant SSPCMs could be potentially applied in the areas of thermal energy storage and temperature-control. (C) 2014 Elsevier Ltd. All rights reserved.