In this work a new solution-based calorimetry approach for determination of the sublimation and vaporization enthalpies of low volatile compounds was proposed. The approach is based on the measurement of solution enthalpy of a molecule of interest in benzene and as well as the measurement of molar refraction index for this molecule. Enthalpies of solution at infinite dilution in benzene for a set of 18 aromatic and polyaromatic hydrocarbons were measured at 298.15 K. Experimental data on vaporization/sublimation enthalpies for this set were collected from the literature. For validation of the literature data additional sublimation experiments were performed for phenanthrene, 1-phenylnaphthalene, 1,2-diphenylbenzene, 1,2,3,4-tetraphenylnaphthalene, hexaphenylbenzene, and rubrene using transpiration, quartz crystal microbalance, and thermogravimetry. Vaporization/sublimation enthalpies derived from the solution calorimetry approach were in good agreement (within experimental uncertainties) with those measured by conventional methods. The solution-based calorimetry approach gives a reliable and quick appraisal of vaporization/sublimation enthalpies. This approach constitutes a complementary additional thermochemical option for vaporization/sublimation enthalpies data evaluation as well as for rapid data gathering for low volatile and/or thermally unstable organic compounds. (C) 2014 Elsevier B.V. All rights reserved.