Schiff bases, the Amadori and Heyns rearrangement products are the most important isomeric intermediates involved in the early Maillard reaction; distinguishing between them by analytical mass spectroscopic techniques remains a challenge. Here we demonstrate that MS/MS fragmentation patterns can be used for the discrimination between glucose derived Schiff bases, Amadori, and Heyns compounds with glycine. An ESI-qTOF-MS system operated in the positive mode under both acidic and neutral conditions was employed to generate unique MS/MS fragmentation patterns of the molecules. Analysis of the MS data has indicated that acidic medium is suitable for generating characteristic and diagnostic ions. At high collision energy (20 eV), the spectrum of Schiff base was largely uninformative, whereas both Amadori and Heyns compounds undergo characteristic fragmentations with high diagnostic value. At low collision energy values (10eV), we observed formation of prominent diagnostic ions from the Schiff base precursor, as well as extensive dehydration reactions of all three molecules. Under acidic conditions, the diagnostic fragmentation pattern of the Amadori compound featured consecutive dehydration reactions. At higher values (20 eV) it underwent the α-fission at the carbonyl group and produced a prominent diagnostic ion [AA + H + CH2]+ at m/z 88. The Schiff base was found to preferentially undergo the retro-aldol degradation and produce diagnostic ions at m/z 118 [AA + H + diose]+ and m/z 140 [AA + Na + diose]+, together with their sugar complements at m/z 85 [tetrose + H-2H2O]+ and m/z 143 [tetrose + Na]+. In the case of Heyns compound, several diagnostic ions were also detected, including the ions at m/z 154 [M + H-2H2O-C2H4O2]+, m/z 170 [AA + Na + triose]+ and m/z 142 [AA + H + Furan]+.