Paraffin waxes have been used in many latent thermal energy storage applications because of their advantageous thermal performances. In this paper, the liquid–solid phase diagram of the binary system of tetradecane and hexadecane has been used to obtain information of the phase transition processes for cool storage applications. The analysis of the phase diagram indicates that, except for the minimum-melting point mixture, all mixtures melt and freeze in a temperature range and not at a constant temperature. The latent heat of fusion evolves throughout this temperature range. Differential scanning calorimetry (DSC) was used to determine the thermophysical properties of the binary system. Depending on the DSC settings throughout the measurements, varying results were obtained. For example, when the DSC runs at a high heating/cooling rate, it will lead to erroneous information. Also, the correct phase transition temperature range cannot be obtained simply from DSC measurement. By combining phase equilibrium considerations with DSC measurements, a reliable design method to incorporate both the heat of phase change and the temperature range is presented.