We review firstly the specificities of the different types of dentin present in mammalian teeth. The outer layers include the mantle dentin, the Tomes' granular and the hyaline Hopewell-Smith's layers. Circumpulpal dentin forming the bulk of the tooth, comprises intertubular and peritubular dentin. In addition to physiological primary and secondary dentin formation, reactionary dentin is produced in response to pathological events. Secondly, we evaluate the role of odontoblasts in dentin formation, their implication in the synthesis and secretion of type I collagen fibrils and non-collagenous molecules. Thirdly, we study the composition and functions of dentin extracellular matrix (ECM) molecules implicated in dentinogenesis. As structural proteins they are mineralization promoters or inhibitors. They are also signaling molecules. Three different forms of dentinogenesis are identified: i) matrix vesicles are implicated in early dentin formation, ii) collagen and some proteoglycans are involved in the formation of predentin, further transformed into intertubular dentin, iii) the distal secretion of some non-collagenous ECM molecules and some serum proteins contribute to the formation of peritubular dentin.