Fatty alcohol and fatty acid compounds are responsible for some significant characteristics of pharmaceuticals, cosmetics, and food products, such as texture and stability. A knowledge of the solid-liquid equilibrium (SLE) behavior of such mixtures is necessary to enhance production processes as well as to upgrade their home and industrial usage. In this study, the SLE phase diagrams of five binary mixtures composed of fatty alcohol compounds and fatty acids, namely, 1-dodecanol, 1-tetradecanol, 1-hexadecanol, lauric acid, myristic acid, and palmitic acid, were determined using differential scanning calorimetry (DSC). A polarized light microscope was used to complement the characterization of phase diagrams, which have shown complex global behavior with eutectic and peritectic points as well as solid solution formation. The SLE data were fitted using the Margules 2-suffix and Margules 3-suffix and the UNIFAC and UNIFAC Dortmund models. The modeling approach using the Margules 3-suffix equation best represented the experimental data.