The fluoroapatite minerals, Ca5-F(PO4)3usually contain some hydroxyis, instead of fluorine. From infrared spectra it was concluded, that there are weak hydrogen bonds OH … F along apatite hexagonal axis1. In order to receive more detailed information about the character of F−and OH−bonds with the nearest atoms in apatites we studied the nuclear magnetic resonance (NMR) spectra of protons and fluorines in natural apatite single crystal, in which approximately 15% of fluorines is substituted by hydroxyis.