The thermodynamic properties of unsubstituted, mono-, and di-substituted toluene derivatives and benzylic radicals with hydroxy, methoxy, formyl, vinyl, methyl, and ethyl substituents are calculated with the bond additivity corrected (BAC) post-Hartree-Fock CBS-QB3 method. Benson's group additivity (GA) scheme is extended to toluene derivatives by determining six group additive value (GAV) and five non-nearest neighbor interaction (NNI) parameters through least-squares regression to a database of thermodynamic properties of 168 compounds and to benzylic radicals by defining 6 GAV and 14 NNI parameters based on a set of 168 radicals. Comparison between CBS-QB3/BAC and GA-calculated thermodynamic values shows that the standard enthalpies of formation generally agree within 4 kJmol(-1), whereas the entropies and the heat capacities generally deviate <4 Jmol(-1) K-1. (c) 2018 American Institute of Chemical Engineers AIChE J, 64: 3649-3661, 2018