The chemical nature of the interface between dentin and adhesive resin materials was characterized by micro-Raman spectroscopy. The resulting chemical profiles were correlated with photomicrographs obtained by SEM after an argon-ion-beam etching treatment of the sample surface. Two commercially available dentin adhesive systems, of which one was also applied with a different conditioning agent, were investigated. Raman spectra, which were recorded along line scans across the interface with a step increment of 1 μm, revealed that resin effectively penetrated 4 to 6 μm deep into the superficially decalcified dentin zone. Across the interface, a gradual transition from resin to dentin over the interdiffusion zone with a mixed contribution of both substances was noticed. Finally, resin appeared to penetrate to the entire decalcification depth of dentin regardless of the aggressiveness of the conditioning procedure.