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This experimental investigation presents the two major aspects of thermal energy storage materials. One is development of eutectic mixtures of polyethylene glycols (PEGs) and another is thermal reliability of them. The commercial grade PEGs with molecular mass 2000 and 10000 were mixed in different mass fractions via facile incorporation method for preparing the eutectic mixtures. The thermal energy storage capacity was measured by using differential scanning calorimeter (DSC) and Fourier transform and infrared spectroscopy (FT‐IR) was adopted to analyse the variation in chemical compositions of eutectics. The eutectics were prepared in the step of 10% mass fraction and characterization show that the mixture of 20% PEG 2000 and 80% PEG 10000 possess the maximum latent heat of fusion, which is 185 kJ/kg. The prepared eutectic mixture was also tested for its durability by in‐house designed thermal cycling tester. The results revealed that this eutectic is able to retain its thermal and chemical properties even after 1500 melting and freezing cycles. The findings of this study show that the prepared binary eutectics are able to be used as potential candidates for passive solar thermal management purposes. [ABSTRACT FROM AUTHOR]