Excess molar enthalpies of the ternary system {x(1) propyl propanoate + x(2) hexane + (1 - x(1) - x(2)) benzene} and of their binary mixtures {x(1) propyl propanoate + x(2) hexane}, {x(1) propyl propanoate + x(2) benzene}, and {x(1) hexane + x(2) benzene} have been determined at 298.15 K and 308.15 K and atmospheric pressure, over the whole composition range. The excess molar enthalpies were measured using a Calvet microcalorimeter. The experimental values were compared with the results obtained with empirical expressions for estimating ternary properties from binary data.