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The study aimed to evaluate the effect of using sourdough or yeast as a leavening agent for French bread making on the Maillard reaction and the bifidogenic effect. Sugars, proteins, and free asparagine were quantified in bread dough before and after fermentation. The levels of the Maillard reaction precursors were very different depending on the leavening agent used, which affected the Maillard reaction during baking. Strecker degradation was favored in the crust of sourdough bread (SB), generating about 7 times more aldehydes than in the crust of yeast bread (YB), thus improving the sensory quality of the bread. In the YB crust, the melanoidization pathway was predominant. The bifidogenic effect of crust and crumb from both breads was evaluated through the in vitro growth of Bifidobacterium adolescentis. SB showed a higher bifidogenic effect, probably due to its composition more favorable for bacteria growth.