The Maillard reaction network with focus on the chemistry of dicarbonyl structures causes considerable interest of research groups in food chemistry and medical science, respectively. Dicarbonyl compounds are well established as the central intermediates in the nonenzymatic browning reaction and have been verified to be responsible for advanced glycation endproduct (AGE) formation. A multitude of Maillard dicarbonyls covering the range of the intact carbon backbone down to C(3) and C(2) fragments were detected in several carbohydrate systems, for example, in glucose, maltose, or ascorbic acid reactions. By definition, dicarbonyls with a C(2)-C(5) carbon backbone must originate by fission of the original carbon skeleton. The present review deals with the five major mechanisms reported in the literature for dicarbonyl decomposition: (i) retro-aldol fragmentation, (ii) hydrolytic α-dicarbonyl cleavage, (iii) oxidative α-dicarbonyl cleavage, (iv) hydrolytic β-dicarbonyl cleavage, and (v) amine-induced β-dicarbonyl cleavage.