The reactivity of the surface of calcium hydroxyapatite (CaHAp) and fluorapatite (CaFAp) was tested and compared by grafting the 1-octylphosphonic dichloride (C8H17OPCl2) using a molar ratio x = 2 or 4, x = n(organic)/n(apatite). Successful synthesis was confirmed by different characterisation techniques such as X-ray powder diffraction patterns, IR spectroscopy, MAS-NMR (H-1 and P-31) and chemical analysis. The difference between their specific surface area (SSA: 57.46 for HAp and 12.09 m(2)/g for FAp), the percentage of carbon measured after treatment with (C8H17OPCl2) and the intensities of IR bands attributed to the grafted moiety suggests that the surface of hydroxyapatite is more reactive than that of fluorapatite. The P-31 CP-MAS-NMR spectra of treated fluorapatite show a significant change in isotropic signal due to the protonation and deprotonation of superficial phosphate group. This can be explained by the difference in the nature of inorganic material. (C) 2011 Elsevier B.V. All rights reserved.