The CaO-P2O5-B2O3 phase diagram was investigated at 1200degreesC in order to determine the existence domain of pure apatitic oxyborophosphates with the general formula Ca-x(PO4)(y)BzOt. The prepared compounds were chemically analyzed and then characterized by X-ray diffraction, infrared absorption and Raman scattering spectroscopies. B-11 and P-31 magic angle spinning (MAS) NMR experiments suggest that boron is introduced as 2-fold coordinated boron BO2- in the channels of the apatitic structure and as triangular BO33- groups in the channels and substituting for PO4 groups. The present data show that a continuous solid solution is obtained inside the apatitic defined domain. (C) 2003 Elsevier Science B.V. All rights reserved.