Magnesium-substituted calcium phosphates with the general formula Ca10-xMgx(PO4)(6)(OH)(2) (x < 1) are synthesized and characterized by IR spectroscopy and x-ray diffraction. The magnesium ion is found to destabilize the structure of hydroxyapatite: increasing the Mg content from I to 10 at. % (in terms of metals) reduces the temperature of the hydroxyapatite-whitlockite transition.