Nanocrystalline apatites exhibit a very fragile structured hydrated surface layer which is only observed in aqueous media. This surface layer contains mobile ionic species which can be easily exchanged with ions from the surrounding fluids. Although the precise structure of this surface layer is still unknown, it presents very specific spectroscopic characteristics. The structure of the hydrated surface layer depends on the constitutive mineral ions: ion exchanges of HPO4 2- ions by CO3 2- ions or of Ca2+ by Mg2+ ions result in a de-structuration of the hydrated layer and modifies its spectroscopic characteristics. However, the original structure can be retrieved by reverse exchange reaction. These alterations do not seem to affect the apatitic lattice. Stoichiometric apatite also shows HPO4 2- on their surface due to a surface hydrolysis after contact with aqueous solutions. Ion exchange is also observed and the environments of the surface carbonate ions seem analogous to that observed in nanocrystalline apatites. The formation of a hydrated layer in aqueous media appears to be a property common to apatites which has to be taken into account in their reactivity and biological behavior.