The discovery of new eutectic phase change materials (PCMs) will overcome the current PCM challenges such as nonbiodegradability, super-cooling, and limited thermal stability. This paper reports on the development of new bio-based PCMs composed of binary mixtures of fatty acid esters and fatty alcohols at their eutectic compositions, which provide potential solid-liquid PCMs for building applications. Six binary systems, namely 1-dodecanol (DD) + methyl stearate (MES), DD + methyl palmitate (MEP), DD + methyl laurate (MEL), 1-tetradecanol (TD) + MES, TD + MEP, and TD + MEL were prepared and their thermal behaviours were deliberated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), long-term thermal stability test, and mass loss analysis. Amongst the studied systems, phase change transition temperature and latent heat of fusion of the eutectic mixtures of DD-MES, DD-MEP, TD-MES, and TD-MEP were found to be suitable for the building application with values of 22.46°C/201.91 J/g, 20.34°C/224.45 J/g, 32.05°C/209.38 J/g, and 26.72°C/210.15 J/g, respectively. The average degree of super-cooling for all PCMs was below 2°C, and no significant changes in thermophysical properties of the developed PCMs were observed after 1000 thermal cycles.