Abstract Fatty alcohols and fatty acids are used in the cosmetic, pharmaceutical and food industries as surfactants. They are also considered phase change materials for thermal storage processes. Information on their thermal properties is required for optimizing production processes as well as for improving their industrial and home use. In the present study, the solid–liquid phase diagrams of three binary systems of 1-tetradecanol+dodecanoic acid, 1-hexadecanol+tetradecanoic acid and 1-octadecanol+hexadecanoic acid were determined by differential scanning calorimetry. The phase-transition phenomena were further investigated by optical micrographs and X-ray diffraction patterns. The experimental data showed that the systems present eutectic transitions and some of them exhibit partial solid phase miscibility. The liquid phase activity coefficients were calculated by Margules 2 and 3-suffix and by UNIFAC and UNIFAC-Dortmund methods. The modeling approach resulted in an accurate prediction, with average absolute deviations from experimental data lower than 1.16K. The values of excess Gibbs free energy present an unusual behavior, with positive deviations at very low alcohol concentrations and negative ones at high concentrations of this component. This occurs due to changes in the H-bonding interactions along the concentration range of the mixture.