Broa is a Portuguese maize bread with characteristic sensory attributes that can only be achieved using traditional maize varieties. This study intends to disclose the volatile compounds that are mainly associated with the baking process of broas, which can be important contributors to their aroma. Twelve broas were prepared from twelve maize flours (eleven traditional maize varieties and one commercial hybrid). Their volatile compounds were analyzed by GC×GC–ToFMS (two-dimensional gas chromatography coupled with time-of-flight mass spectrometry) for an untargeted screening of the chemical compounds mainly formed during baking. It was possible to identify 128 volatiles that belonged to the main chemical families formed during this stage. Among these, only 16 had been previously detected in broas. The most abundant were furans, furanones, and pyranones, but the most relevant for the aroma of broas were ascribed to sulfur-containing compounds, in particular dimethyl trisulfide and methanethiol. Pyrazines might contribute negatively to the aroma of broas since they were present in higher amounts in the commercial broa. This work constitutes the most detailed study of the characterization of broas volatile compounds, particularly those formed during the Maillard reaction. These findings may contribute to the characterization of other maize-based foodstuffs, ultimately improving the production of foods with better sensory features.