The interaction of polyaniline with alkylsulfonate dopants have been investigated at the atomic level using quantum mechanical methods. Calculations have been performed on complexes formed by dopant molecules with an alkyl group ranging from methyl to nonyl and model oligoanilines of different sizes. The stabilization provided by the formation of the alkylsulfonate···oligoaniline complexes (70−90 kcal/mol) is significantly higher than that found for conventional hydrogen bonds (5−12 kcal/mol) but lower than that obtained for methylsulfate···alkylammonium and methylsulfate···Na+ systems (120−135 kcal/mol). On the other hand, the influence of size of the alkyl group contained in the dopant on the interaction is practically negligible, whereas, in opposition, the number of aniline units used to represent polyaniline significantly affects the energetics of the interaction. Specifically, the interaction energy of an alkyl-dopant molecule and an infinite polyaniline chain has been predicted to be around −65 kcal/mol. The overall results allow the conclusion that the interaction between alkylsulfonate dopants and polyaniline is a very local phenomenon.