A self-consistent estimation method for the thermochemical properties of polycyclic aromatic hydrocarbons (PAH) is presented. This method is based on enthalpies of formation (DeltaH(f)(o)), entropies (S-298(o)), and heat capacities (C-p(o)) obtained from B3LYP/6-31 G(d) calculations of the total energies and frequencies for 139 PAHs, including C-60 and C-70 fullerenes. The enthalpies of formation were calculated using an optimized set of homodesmic reactions given the available experimental DeltaH(f)(o) of PAHs. The theoretical entropies were compared with the existing experimental entropies, and some inconsistencies in the experimental data were identified. The estimation method presented here is a systematic extension of the widely employed atom-centered group additivity method originally proposed by Benson. This new method is based on bond-centered groups that define bonds linking two atom-centered groups and specify the size of the rings to which they belong. In addition, a term to describe the resonance energy is included. The thermochemical properties of PAHs UP to C-70 fullerene are estimated with a mean average deviation of 2.8 kcal mol(-1) in DeltaH(f)(o) 0.7 cal K-1 mol(-1) in S-298(o), and about 0.5 cal K-1 mol(-1) in the C-p(o). This bond-centered group additivity method for the thermochemical properties of PAHs significantly expands both the range of systems that can be estimated and the accuracy of the estimations. The results of this work also allow us to assess the quality of available experimental data. For example, there are strong indications that the literature DeltaH(f)(o) of benzo[k]fluoranthene is about 10 kcal mol(-1) too low.