Alkali is an indispensable additive in Chinese steamed bread (CSB) production. This work aimed to evaluate the key roles of alkali in the microbial community of dough fermented using Chinese traditional starter (CTS) and the aroma profiles of CSB. The dominant fungi in CTS and fermented dough were members of the phylum Ascomycota and the genus Saccharomyces. Pediococcus, Companilactobacillus, and Weissella were the dominant bacterial genera in CTS and fermented dough. Adding alkali could retain the types of dominant yeasts and LAB derived from CTS, decrease the relative abundance of Companilactobacillus crustorum and Weissella cibaria, and increase that of Pediococcus pentosaceus, in fermented dough. Principal component analysis (PCA) indicated that adding alkali decreased the content of sourness-related volatiles in CSB fermented by CTS. Correlation analysis showed that Pediococcus and Weissella in fermented dough were positively correlated with the lipid oxidation flavor-related compounds in CSB, and Lactobacillus was positively correlated with sourness-related aroma compounds. Synthetic microbial community experiments indicated that CSB fermented by the starter containing P. pentosaceus possessed a strong aroma, and adding alkali weakened the flavor intensity. Alkali addition could promote the formation of ethyl acetate and methyl acetate with a pleasant fruity aroma in W. cibaria-associated CSB.