Even if mechanical bonding to enamel utilizing the acid-etch technique has been very successful, adhesion to dentin is still a challenge to researchers and clinicians. Dentin is a vital tissue and differs in composition from enamel: acid-etching does not enhance the bond strength of composite resins to dentin and may elicit a severe pulpal response. For an effective bond to occur, a dentin bonding system has to be used. The first generation of methacrylate-based dentin adhesives was capable of chemical bonding to the inorganic phase of dentin. The chemical basis for this resin-dentin adhesive was the interaction between a phosphate group attached to the methacrylate and the calcium ions on the dentin surface. This system yielded rather low bond strengths which were clinically unsatisfying. The second generation of dentin adhesives became available to the profession recently. Each of these new bonding systems use similar chemical composition for the same purpose of bonding with physicochemical interaction to the hard tooth tissues. All these systems contain a mild acid dentin conditioner to remove the smear layer and an aqueous resin containing primer to improve monomer penetration into the hydrophilic dentin surface. The second generation dentin bonding systems are extremely sensitive to variations upon the completeness of instructions and how accurately these are followed by dental practitioners.