For the application of the freezing logistics, a composite phase change material (PCM) which was composed of trimethylolpropane (TMP), ammonium chloride (NH4Cl) and H2O was proposed as the research object. The composite materials with different ratios were measured by using differential scanning calorimetry (DSC), and a composite PCM with excellent thermal performance was selected, which had a mass ratio of 1.0: 2.0: 7.0 (TMP: NH4Cl: H2O). The PCM with phase-change temperature of -19.4 °C and latent heat enthalpy of 250.5 kJ/kg was developed, and the effects of cooling rate, cooling medium temperature and vessel diameter on the supercooling degree were investigated. The results showed that the supercooling degree can be effectively reduced by reducing the cooling rate of the phase change material, increasing the temperature of the cooling medium and the size of the container.