Metal ions are known to influence the course of the Maillard reaction through formation of various complexes such as bis(amino acids), these complexes are known to undergo more facile reaction with sugars. Due to this enhanced reactivity, the possible formation of di-glycated amino acids in glucose/alanine model systems with and without FeCl2 was investigated using isotope labelling technique in conjunction with ESI/qTOF/MS/MS. Forty-eight derivatives of bis[N,N'-di-glycated alanine] iron(II) complexes were tentatively identified. These complexes incorporated one iron atom, two [13C-3] atoms from alanine and up-to twenty-four carbon atoms from glucose [13C-U], were incorporated as triose (C3), tetrose (C4), pentose (C5) or hexose (C6) moieties. Furthermore, the dissociation of the above complexes released variously substituted N,N-di-glycated alanine derivatives incorporating one alanine [13C-3] atom and up to twelve carbon atoms from glucose [13C-U]. The MS/MS analysis of diglycated alanines indicated that they follow similar fragmentation pathways as Amadori product of alanine.