The molar excess volumes v(E) of the three binary mixtures methyl decanoate + n-alkane (n-dodecane, n-tetradecane, and n-hexadecane) were measured at temperature T = 298.15 K and atmospheric pressure using a vibrating tube densitometer. Furthermore, the molar excess enthalpies h(E) of the six binary mixtures methyl decanoate + n-alkane (n-hexane, n-octane, n-decane, n-dodecane, n-tetradecane, and n-hexadecane) were measured at the same ambient conditions using a Calvet microcalorimeter. Both excess properties showed an increase with the increasing chain length of the n-alkane. Two equations of state, that is, a heterosegmental approach of Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) and SAFT-gamma Mie, were applied to predict the excess properties of the respective binary mixtures. Very satisfying agreement between the experimental data and modeling results was obtained for both equations of state.