Ion mobility spectrometry (IMS) and IMS/MS techniques were used to differentiate between nitrogenprotonated and carbon-protonated anilines, both of which coexist under the conditions of the IMS. Analysis of the results led to the conclusion that the former species had lower mobilities than the latter. This was attributed mainly to charge delocalization in the ring-protonated species, which results in a weaker interaction with the drift gas molecules. Furthermore,meta-alkyl substitution enhanced ring protonation, while in 2-chloroaniline the nitrogenprotonated species was predominant, as expected.