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Along with the heat transfer mechanism for the development of a latent heat storage unit (LHSU), the choice of the phase change material (PCM) plays an important role. The enviable thermo-physical, kinetic, and chemical properties of PCM with the economy is an essential criterion for efficient thermo-economical LHSU. The most important criteria that have limited widespread use of LHSU are the useful life of phase change materials. For long term performance of LHSU, the PCM used in the system should be thermally stable and reliable. It does not deteriorate its own properties, especially latent heat and melting point after a repeated number of thermal cycles. Thus an exhaustive literature survey is carried out for different types of PCMs used. The primary objective of this chapter is to carry out a critical review of thermal stability of different group of PCM especially for low temperature applications. Further, an extensive list of different PCMs which are undergone thermal cyclic tests by different researchers is prepared. This information is towards the selection of reliable PCM for latent heat storage unit.