In this study, novel polyethylene glycol @ Si3N4 nanowires as phase-change materials (PCMs) were developed by using ultrasonic cell disruptor. The results obtained herein indicate that these nanowires can be a potential carrier for preparing PCMs. The results show that PEG is composited in a fluffy nano-network structure of Si3N4 nanowires, which could not be easily leaked from this structure for the solid–liquid phase transition. X-ray diffraction and Fourier transform infrared spectroscopy were employed for investigating the structures of PCMs; the results show that a chemical reaction does not occur between PEG and Si3N4 nanowires. Differential scanning calorimetry analysis results indicated that PCMs exhibit appropriate phase-change temperature and excellent high-phase change enthalpy. From the TGA results, PCMs exhibit perfect thermal stability. The PCMs could perfectly maintain their phase transition after 100 melting–freezing cycles. The thermal conductivity of PCMs-1 was 0.362W/(mK), which was enhanced by 88.54% in comparison with that to pure PEG. The heat storage or release rate of PCMs is significantly more rapid than that of pure PEG for practical applications.