Hydroxyapatite nanocrystals synthetized in the presence of different concentrations of magnesium and fluoride ions in solutions I, 5 and 10 at.% have been submitted to a structural and chemical characterization. The syntheses were carried out in the presence of low molecular weight polyacrilic acid, which has been verified to inhibit hydroxyapatite crystallization. The polyelectrolyte is adsorbed into the crystals during the synthesis and provokes a reduction of the mean crystal sizes. The reduction is greater along the direction orthogonal to the c-axis, suggesting a preferential adsorption of the polyelectrolyte on the crystalline faces parallel to the c-axis. Both magnesium and fluoride can be incorporated into the hydroxyapatite structure. On the basis of the values of the lattice constants and of the magnesium relative content of the solid phase, it can be suggested that probably just a part of magnesium is substituted for calcium, the remainder being adsorbed on the crystal surface. However, magnesium destabilizes the apatitic structure favouring its thermal conversion into p-tricalcium phosphate, and displays an inhibiting effect on the crystallization of hydroxyapatite. This last effect is enhanced by the simultaneous presence of polyacrylic acid. Fluoride substitution for hydroxyl ions into hydroxyapatite structure induces a slight increase of the crystal sizes along the c-axis direction. The data indicate that the experimental approach can be successfully used to prepare nanoapatite with crystallinity, crystal dimensions, composition, structure and stability very close to those characteristic of biological apatites. (C) 1998 Elsevier Science Inc. All rights reserved.