This study was conducted to improve the quality and theoretical understanding of gluten-free sorghum bread. The addition of 2% hydroxypropyl methylcellulose improved bread based on 105% water, 70% sorghum flour, and 30% potato starch. Nevertheless, a flat top and tendency toward a hole in the crumb remained. Sourdough fermentation of the total sorghum flour eliminated these problems. Size-exclusion high-performance liquid chromatography demonstrated that during sourdough fermentation, proteins from the dough liquid were degraded to peptides smaller than kafirin monomers (<19 kDa). Laser scanning confocal microscopy showed aggregated protein in bread crumb without sourdough fermentation, whereas with sourdough fermentation, only small isolated patches of protein bodies embedded in matrix protein remained. In oscillatory temperature sweeps, sourdough fermentation caused a significantly higher resistance to deformation (|G*|) after gelatinization of the above batter relative to batters without sourdough. Results suggest that a strong starch gel, without interference of aggregated protein, is desirable for this type of bread.