Benzoxazinoids (BXDs) are plant specialized metabolites exerting a pivotal role in plant nutrition, allelopathy, and defenses. Multihexose benzoxazinoids were previously observed in cereal-based food products such as whole-grain bread. However, their production in plants and exact structure have not been fully elucidated. In this study, we showed that drought induced the production of di-, tri-, and even tetrahexose BXDs in maize roots and leaves. We performed an extensive nuclear magnetic resonance study and elucidated the nature and linkage of the sugar units, which were identified as gentiobiose units β-linked (1″ → 6′) for the dihexoses and (1″ → 6′)/(1‴ → 6″) for the trihexoses. Drought induced the production of DIMBOA-2Glc, DIMBOA-3Glc, HMBOA-2Glc, HMBOA-3Glc, and HDMBOA-2Glc. The induction was common among several maize lines and the strongest in seven-day-old seedlings. This work provides ground to further characterize the BXD synthetic pathway, its relevance in maizeenvironment interactions, and its impact on human health.