The site of protonation for gas-phase aniline has been debated for many years, with many research groups contributing experimental and computational evidence for either the amino-protonated or the para-carbon-protonated tautomer as the gas-phase global minimum structure. Here, we employ differential mobility spectrometry (DMS) and mass spectrometry (MS) to separate and characterize the amino-protonated (N-protonated) and para-carbon-protonated ( p-protonated) tautomers of aniline. We demonstrate that upon electrospray ionization (ESI), aniline is protonated predominantly at the amino position. Similar analyses are conducted on another three isotopically labeled forms of aniline to confirm our structural assignments. We observe a significant reduction of the relative population of the p-protonated tautomer when a protic ESI solvent is employed (methanol/water) compared to when an aprotic solvent (acetonitrile) is employed. We also observe conversion of the p-protonated species into the N-protonated species upon clustering with protic solvent vapor post-DMS selection-a finding supported by previous experimental data acquired using DMS-MS.