The enthalpies of vaporization/sublimation of 2-, 3- and 4-methyl-acetophenones and 2-, 3-, 4-cyano-acetophenones were derived from the vapor pressure temperature dependence measured with help of the gas saturation method. Enthalpies of fusion of 4-methyl-acetophenone and 2-, 3- and 4-cyano-acetophenone were measured by using DSC. The literature thermochemical data for methyl-, ethyl, cyano- and acetoxy-substituted acetophenones and new results were evaluated using structure–property correlations. The G* quantum chemical methods were validated for reliable estimation of the enthalpies of formation of substituted acetophenones in the gaseous state. The evaluated thermodynamic data were used to design the “centerpiece” method for the assessment of enthalpies of formation and enthalpies of vaporization of substituted benzenes.Graphical abstract