The purpose of this study was to investigate the interfacial interaction of tartaric acid with hydroxyapatite and enamel. Hydroxyapatite particles were mixed with 15% (w/v) alcohol-aqueous (1:1) solution of tartaric acid for 72 h. After the mixture, the filtrate was separated from the solid. The filtrate, the solid, hydroxyapatite, and tartaric acid were dried for FTIR and XRD analysis. Enamel disks etched with tartaric acid for 60 s were analyzed by attenuated total reflectance (ATR). Enamel disks etched with 15% tartaric acid for 15, 30, 60, 120 s were analyzed by SEM. FTIR spectra showed carboxylate in the solid and in subtraction spectra. ATR spectra revealed carboxylate on the enamel surfaces. XRD data indicated the formation of calcium tartrate and calcium hydrogen phosphate after the reaction of tartaric acid with hydroxyapatite. SEM observations revealed typical decalcification of the periphery of the enamel rods due tartaric acid etching. It is concluded that tartaric acid can decalcify and chemisorb onto HA simultaneously, hence, tartaric acid could be used as etchant and ingredient of self-etching primers in adhesive dentistry.