The potential of ion trap mass spectrometry has been evaluated for the characterization and distinction of two isomeric amphetamines drugs, namely N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine and N-ethyl-3,4-methylenedioxyamphetamine. Whereas the electron impact spectra of the two molecules lack specificity, collisional experiments on the ionic species at m/z 72 allows unequivocal distinction between the two isomers. Analogous results are achieved by positive ion chemical ionization and collisional experiments on the protonated molecules. All the different approaches have been successfully applied to the gas chromatography/mass spectrometry analysis of a tablet of illicit drug.