The melting process and the solidifying process of phase change material (PCM) are usually considered symmetrical in the traditional PCM heat transfer models, but there are inevitable calculation errors using these models. In this paper, a new heat transfer model of PCM based on the energy asymmetry was built, and it was validated by experimental data. It was found that the two main reasons for the energy asymmetry of the PCM were the melting temperature range and the solidifying temperature range were not the same and the supercooling problem during the cooling process. No matter for only one thermal cycle or for the multiple thermal cycles, the results from the asymmetrical model and the symmetrical model were different. Apparently, compared with the symmetrical model, the asymmetrical model had higher accuracy, and the heating/cooling process in the asymmetrical model was more consistent with the real heating/cooling process of the PCM.