Five experimental 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-based one-step self-etch adhesives were designed by varying amounts of MDP. The aim of this study was to examine the effect of the quantity of calcium salt of MDP (MDP-Ca) salt produced by demineralization on the bond durability between experimental one-step adhesives and enamel or dentin. Bond strengths of experimental adhesives to the enamel and dentin were measured, before and after 30,000×thermocycling. The fractured enamel and dentin samples as well as the fractured adhesive surfaces obtained during adhesion test were analyzed by a scanning electron microscope and energy-dispersive X-ray microscope. An increase in the amount of MDP-Ca salt to above 37.2 mg/g drastically decreased the dentin bond strength and changed the fracture type during the thermocycling process. In contrast, the enamel bond strength remained unchanged, although the fracture type changed to an interfacial failure with increasing the amount of MDP-Ca salt to 78.3 mg/g.