Tooth enamel is a distinctive nanocomposite with a highly organized hierarchical structure made of nanometer- and micrometer-scale building blocks. This structure has an excellent mechanical function that can last for decades thanks to an effective but underexploited interfacial chemical bonding between the building blocks. In this study, the nanomechanical system test (NST), scanning electron microscope (SEM), X-ray diffraction (XRD, including powder XRD or PXRD, small angle XRD or SAXRD, and grazing incidence small angle XRD or GISAXRD), and atomic force microscope (AFM) have been employed to analyze the water-mediated bonding on the enamel surface. Via the cycling between hydration, dehydration, and rehydration treatments, a reversible change in the interfacial distance (i.e., d-space in the XRD pattern) between hydroxyapatite (HAP) nanocrystallites have been found switchable between the embrittling and toughening on the enamel surface. From the hydrated to the dehydrated conditions, an energy dissipation to deform a unit volume (1 μm3) of biocomposite on the enamel surface and subsurface has decreased by 20%. This finding can help quantify and predict biomineral-surface properties in all humidity and develop new methods to protect tooth enamel of "dry-mouth" patients.