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Dentin bonding systems have been dramatically simplified and improved during the recent decades. Monomer penetration into dentin and its polymerization in situ creates a hybrid layer, which is essential to obtain good bonding to dentin. Moreover, the presence of an acid–base resistant zone below the hybrid layer has been documented with self-etching adhesive systems in an artificial secondary caries attack. When ultrastructure of the acid–base resistant zone is assessed by SEM and TEM observations, formation of the acid–base resistant zone is considered to be due to the monomer penetration potential and fluoride release in the adhesive systems. Natural dentin has a limited potential to resist an acid attack of secondary caries; however, the acid–base resistant zone does not purely consist of dentin in morphology, it is rather a combination of dentin and the adjacent hybrid layer. Therefore, the reinforced dentin has been called “Super Dentin” bearing the ability to prevent primary and secondary caries. Prospectively, the great potential of adhesive technology in creation of the “Super Dentin” would lead to the development of new materials for mechanical, chemical and biological protection of the dental structures.