Solid state phase change materials are considered as potential candidates for thermal energy storage. Among the solid-solid heat storage materials, the most promising heat storage materials are organic polyalcohol globular tetrahedral molecular crystals such as (CH 3)C(CH 2 OH) 3 for PG, (NH 2)C(CH 2 OH) 3 for TRIS, and (CH 3)(NH 2)C(CH 2 OH) 2 for AMPL, which store a large amount of thermal energy in their solid state high temperature phases with orientationally disorder crystal structure. In this study, we obtained the Gibbs energies of pure PG and pure TRIS derived utilizing the available experimental data including temperature-dependency of heat capacity, enthalpy, and transitions temperatures, as well as obtained optimized binary phase diagrams of TRIS-PG and AMPL-PG by CALPHAD calculations. The phase boundaries are verified by in-situ X-ray diffraction (XRD). Optimized database of these two binaries will allow exploration of ternary and higher order systems using CALPHAD methodology that will provide a wider selection of materials for practical thermal energy storage applications. Regular and sub-regular solution models are used for calculations in which the excess Gibbs energies are expressed by the Redlich-Kister-Muggianu polynomial. A set of self-consistent interaction parameters formulating the Gibbs energies of various phases in binary systems are obtained. The TRIS-PG binary phase diagram was calculated from room temperature to the liquid phase temperature, the modeled phase diagram and the experimental data from our work are in good agreement. We also used experimental data of TRIS-PG from the literature which shows a good agreement between the two data sets. Our optimized TRIS-PG phase diagrams show a wider solid-state two phase region, where there is demixing of phases, whereas the calculations from the literature show a very narrow region. We also present optimized AMPL-PG binary phase diagram using PARROT module in Thermal-Calc