In this research, the effect of selenium (Se) enrichment on dough fermentation characteristics of yeast and the possible mechanisms was investigated. Then, the Se-enriched yeast was used as starter to make Se-enriched bread, and the difference between Se-enriched bread and common bread was investigated. It was found Se enrichment increased CO2production and sugar consumption rate ofSaccharomyces cerevisiae(S. cerevisiae) in dough fermentation, and had positive impacts on final volume and rheological index of dough. The mechanism is possibly related to higher activity and protein expression of hexokinase (HK), phosphofructokinase (PFK), pyruvate kinase (PK), citrate synthase (CS), isocitrate dehydrogenase (ICD), and α-ketoglutarate dehydrogenase (α-KGDHC) in Se-enriched yeast. Moreover, Se-enriched bread (Se content: 11.29 μg/g) prepared by using Se-enriched yeast as starter exhibited higher overall acceptability on sensory, cell density in stomatal morphology, and better elasticity and cohesiveness on texture properties than common bread, which may be due to effect of higher CO2production on dough quality. These results indicate Se-enriched yeast could be used as both Se-supplements and starter in baked-foods making.