ABSTRACT This study examined the fermentation mechanism of Gansu starter cultures (GSSC) and Henan starter cultures (HNSC), each mixed with yeast, in enhancing the distinctive flavor of bread. High‐throughput sequencing analysis revealed that 157 bacterial genera and 53 fungal genera were identified in the GSSC, while the HNSC comprised 29 bacterial genera and 35 fungal genera. The data confirmed that the levels of lactic acid and exopolysaccharides (EPS) increased during the mung bean sourdough fermentation process with GSSC and HNSC, contributing to improved dough fermentation properties. The results of scanning electron microscopy and disulfide bond analysis indicated improved gluten network formation in Gansu mung bean dough (GMD) and Henan mung bean dough (HMD). The FT‐IR data revealed that Gansu mung bean sourdough bread (GMB) and Henan mung bean sourdough bread (HMB) each exhibited a stable protein secondary structure, which enhanced specific volume and texture property. Specifically, the specific volume of GMB and HMB increased by 35.38% and 67.69%, respectively, compared to the regular mung bean bread. Gas chromatography‐ion mobility spectrometry (GC‐IMS) analysis of bread identified 42 key volatile compounds. Correlation analysis showed that GMB developed citrus and burnt popcorn aromas, while HMB presented fruity and floral notes. These new findings would provide theoretical basis for using new starter cultures for enhancing both the quality and flavor of mung bean bread.