A novel solid-solid phase change materials was synthesized by the two-step condensation reaction of polyethylene glycol (PEG1000), neopentyl glycol (NPG) and 4, 4-diphenylmethane diisocyanate (MDI). Polyethylene glycol (PEG1000) was used as soft segment and 4, 4-diphenylmethane diisocyanate (MDI) as hard segment. The composition, structure and phase change properties were characterized by Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), polarization optical microscopy (POM) respectively. The results indicated that the PCM appeared typical solid-solid phase transition property and the phase change enthalpy and phase transition temperature reached to 120.45 J/g and 37.32°C, respectively.