Molar excess enthalpies, H(m)(E), at 298.15 K and atmospheric pressure have been determined over the entire mole fraction range, using a Tian-Calvet microcalorimeter, for the systems: propanone, 2-butanone, 2-pentanone, or 2-heptanone + aniline or + N-methylaniline. The negative H(m)(E), values obtained for all of the mixtures reveal that interactions between unlike molecules are prevalent. Aniline solutions show more negative H(m)(E) due to stronger amine-ketone interactions compared to those in N-methylaniline solutions. In addition, H(m)(E), increases with the size of the alkanone, which may be interpreted in terms of a weakening of interactions between unlike molecules. H(m)(E) somewhat differently in N-methylaniline solutions, probably due to the positive contribution to H(m)(E), is here more important. Molar excess internal energies at constant volume, U(Vm)(E), have been determined from the present H(m)(E) using our previous measurements on molar excess volumes, compressibilities, and isothermal expansion coefficients. U(Vm)(E) behaves similarly to H(m)(E). U(Vm)(E) values are much higher than those of HE(m)(E), which remarks the importance of the contribution of the equation of state term to H(m)(E).