Polyurethane phase change material (PUPCM) has been demonstrated to be effective solid-solid phase change material for thermal energy storage. However, the high cost and complex process on preparation of PUPCMs with high enthalpy and broad phase transition temperature range can prohibit industrialscale applications. In this work, a series of novel form-stable paraffin/PUPCMs composites (n-octadecane/PUPCM, n-eicosane/PUPCM and paraffin wax/PUPCM) with high enthalpy and broad phase transition temperature range (20-65 degrees C) were directly synthesized via bulk polymerization. The composites were prepared at different mass fractions of n-octadecane (10, 20, 25, 30% w/w). The results indicated that the maximum encapsulation ratio for n-octadecane/PUPCM10000 composites was around 25% w/w. The chemical structure and crystalline properties of these composites were characterized by Fourier transform infrared spectroscopy (FT-IR), polarizing optical microscopy (POM), wide-angle X-ray diffraction (WAXD). Thermal properties and thermal reliability of the composites were determined using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). From DSC analysis, the composites showed a typical dual phase change temperature. The enthalpy for the composite with 25% w/w n-eicosane was as high as 141.2 J/g. TGA analysis indicated that the composites degraded at considerably high temperatures. The process of preparation of PUPCMs and their composites was very simple, inexpensive, environmental friendly and easy to process into desired shapes, which could find the promising applications in solar energy storage and building. (C) 2013 Elsevier Ltd. All rights reserved.