The resin-dentin interface formed by two dentin adhesives, Optibond (OPTI, Kerr) and Scotchbond Multi-Purpose (SBMP, 3M), was ultramorphologically examined by transmission electron microscopy (TEM). Ultrastructural information from nondemineralized and demineralized sections was correlated. It was hypothesized that the different chemical formulations of the two adhesives would result in a different morphological appearance of the hybrid layer. Ultrastructural TEM examination proved that each of the two dentin adhesive systems was able to establish a micromechanical bond between dentin and resin with the formation of a hybrid layer. However, the interfacial hybridization process that took place to produce this resin-dentin bond appeared to be specifically related to the chemical composition and application modes of both systems. OPTI consistently presented with a hybrid layer with a relatively uniform ultrastructure, electron density, and acid resistance. These three parameters were found to be more variable for the hybrid layer formed by SBMP. Characteristic of SBMP was the identification of an amorphous phase deposited at the outer surface of the hybrid layer. Although both adhesive systems investigated follow a total-etch concept, their specific chemical formulations result in different interfacial ultrastructures that are probably related to different underlying bonding mechanisms. The clinical significance of these morphological findings, however, is still unknown.