A series of diastereomeric 4S,5S,6R/S-tetrahydropyrano- and 3S,4S,5R/S-tetrahydrofuranochromenylamine derivatives (a/b isomers; 1-26) has been studied under electron ionization (EI) and chemical ionization (CI) conditions. The EI mass spectra of all diastereomeric compounds show two characteristic fragment ions, of which one is formed by retro-Diels-Alder (RDA) reaction from the molecular ion, retaining the charge on the diene fragment, and the other [M-(HNAr)]+ ion by a simple radical loss. The RDA process is more favorable in all b isomers, whereas the radical loss is dominant in all a isomers; based on these two ions it is easy to differentiate the two diastereomers. The collision-induced dissociation (CID) spectra of all the molecular ions also show the same trend, which reflects the stereoselectivity in the formation of the two characteristic fragment ions. The results of theoretical calculations performed are in accordance with the experimental observations. The CI experiments (methane and isobutane) on all the diastereomeric compounds also enabled the differentiation of the isomers.