Infrared photodissociation spectra of aniline+–M (M=thiophene, furan and phenol) are measured in the 2700–3700 cm−1 region and analyzed by density functional theory calculations. Only a structure involving a π-type hydrogen bond is found for aniline+–thiophene. Two structural isomers are identified for aniline+–furan and aniline+–phenol, which have either a π-type or a σ-type hydrogen bond, where an amino proton of aniline+ interacts with the π-electrons or the oxygen atom of the neutral molecules, respectively. The isomer with a σ-type hydrogen bond is more stable for aniline+–phenol, while less stable for aniline+–furan.