In this paper, the feasibility of using metal foams to enhance the heat transfer capability of phase change materials (PCMs) in low- and high-temperature thermal energy storage systems was assessed. Heat transfer in solid/liquid phase change of porous materials (metal foams and expanded graphite) at low and high temperatures was investigated. Organic commercial paraffin wax and inorganic calcium chloride hydrate were employed as the low-temperature materials, whereas sodium nitrate was used as the high-temperature material in the experiment. Heat transfer characteristics of these PCMs embedded with open-cell metal foams were studied. Composites of paraffin and expanded graphite with a graphite mass ratio of 3%, 6%, and 9% were developed. The heat transfer performances of these composites were tested and compared with metal foams. The results indicate that metal foams have better heat transfer performance due to their continuous inter-connected structures than expanded graphite. However, porous materials can suppress the effects of natural convection in liquid zone, particularly for PCMs with low viscosities, thereby leading to different heat transfer performances at different regimes (solid, solid/liquid, and liquid regions). This implies that porous materials do not always enhance heat transfer in every regime.