Semiempirical calculations (AM1) together with experimental mass spectrometric (FT-ICR) data indicate the imino nitrogen atom as the favoured site of protonation and the amino nitrogen atom as the site of deprotonation of the amidine group in the gas phase. For tautomerizing N-methyl-N'-phenylbenzamidine the tautomer with the phenyl group at the imino nitrogen atom weakly predominates in tautomeric mixture.