In this work a solution calorimetry approach was applied for determination of the sublimation enthalpies of 9 substituted acetanilides. The solution enthalpies of acetanilide and 9 its derivatives in acetonitrile were measured and solvation enthalpies were calculated by a group-additivity scheme. Additivity of solvation enthalpy due to influence of the substituent on the acidity of the proton of NHCOCH3-group and OH-group was checked with the use of IR-spectroscopy. The sublimation enthalpies obtained from the solution calorimetry approach were compared to the available literature data. In most cases convergence within the limits of experimental uncertainty was demonstrated.