The alkali generation by oral bacteria plays fundamental roles to maintain the balance of microflora and pH of the dental biofilms, and the alkali generation capacity of saliva and plaque was proved to be reversely correlated to the formation of dental caries. Oral alkali generation, which is under the control of multiple environmental factors, is a complex system composed by multiple species and pathways. This paper reviews the major alkali generation pathways in dental biofilms, the correlation of alkali generation to dental caries and the molecular research progress on alkali generation by oral bacteria.