Previous research, in which the bonding effectiveness of the 3 self-etch monomers HAEPA, EAEPA, and MAEPA was determined, showed that MAEPA was most effective. In this study, the molecular interactions of these monomers with hydroxyapatite and dentin were investigated by combining x-ray diffraction, infrared spectroscopy, and scanning electron microscopy. We tested the null hypothesis that the bonding performance of these monomers does not correlate to the formation of monomer-calcium salts and to hydrolytic stability of these monomer-calcium complexes. Monomer/ethanol/water solutions were prepared and applied to synthetic hydroxyapatite and dentin. While HAEPA and EAEPA dissolved dentin considerably and deposited unstable calcium-phosphate salts (DCPD), MAEPA formed hydrolysis-resistant monomer-calcium salts that remained attached to the dentin surface even after being washed. The chemical stability of the monomer-Ca salts was thought to contribute in particular to the bond durability, but this study shows that the formation of stable monomer-calcium salts also enhances the 'immediate' bonding performance of self-etch adhesives.