Abstract With an aim to prepare phase change material (PCM) as self-sustaining film from poly(ethylene glycol) (PEG) having reduced hydrophilicity, cross-linking of PEG and hydroxy-terminated poly(dimethyl siloxane) (HTPDMS) was done by using tetraethyl orthosilicate (TEOS) as a cross-linking agent. Following the confirmation of the crosslinked polymer using FTIR and 13C-solid state NMR, the crystallization properties were studied using X-ray diffraction and polarized optical microscopy. DSC analysis indicated an increase in enthalpy with increasing concentration of PEG. The enthalpy of fusion and crystallization was observed to reach a maximum of 125 and 104 J g−1 respectively. Contact angle of 89.5° has been achieved for polymer with highest concentration of HTPDMS. The material with lowest PEG concentration was film forming in nature. This material can be extensively used as a thermal energy storage material particularly, in smart packaging.