For all dimethylnaphthalenes (DMNs) the transition from a planar ring conformation to a nonplanar one results in energy increase in the range 1.7–2.4kcal/mol. There is a linear relationship between averaged rigidity constant and relative energy of DMNs. The relative stability of DMNs does not follow the aromatic stabilization based on NICS values. The ETS-NOCV analysis shows that more efficient bonding in the π-electron system is the origin of enhanced stability in laterally substituted (CH3, Cl and NO2) naphthalenes. The results for Caryl-CH3 system indicate more steric repulsion in going from 2,7-DMN to 1,8-DMN following the increase of relative energies.