An ab initio study of two series of carbon-to-carbon proton transfer reactions is reported. The first series refers to the heterocyclic C(4)H(5)X(+)/C(4)H(4)X (X = CH(-), NH, S, O, PH, CH(2), AlH, BH) systems, and the second to the linear [Formula: see text] (X = CH(-), NH, S, PH, O, CH(2), AlH, BH) reference systems . The major objective of this study was to examine to what degree the aromaticity of C(4)H(4)X (X = CH(-), NH, S, O, PH) and the antiaromaticity of C(4)H(4)X (X = AlH, BH) is expressed at the transition state of the proton transfer and how this affects the respective intrinsic barriers. From the differences in the barriers between a given cyclic system and the corresponding linear reference system , ΔΔH(++) = ΔH(++)(cyclic) - ΔH(++)(linear), it was inferred that in the cyclic systems both aromaticity and antiaromaticity lower ΔH(++)(cyclic). This conclusion was based on the assumption that the factors not associated with aromaticity or antiaromaticity such as resonance, inductive and polarizability effects in the protonated species, and charge delocalization occurring along the reaction coordinate affect ΔH(++) for the cyclic and linear systems in a similar way and hence offset each other in ΔΔH(++). The extent by which ΔH(++)(cyclic) is lowered in the aromatic systems correlates quite well with the degree of aromaticity of C(4)H(4)X as measured by aromatic stabilization energies as well as the NICS(1) values of the respective C(4)H(4)X. According to the rules of the principle of nonperfect synchronization (PNS), these results imply a disproportionately large degree of aromaticity at the transition state for the aromatic systems and a disproportionately small degree of transition state antiaromaticity for the antiaromatic systems. These conclusions are consistent with the changes in the NICS(1) values along the reaction coordinate. Other points discussed in the paper include the complex interplay of resonance, inductive, and polarizability effects, along with aromaticity and antiaromaticity on the proton affinities of C(4)H(4)X.