A method of determining the stoichiometry of metastable phases from nucleation characteristics is described and is applied to calcium phosphate precipitation. The stoichiometric ratio [Ca]/[P] is shown to be 1.49 ± 0.02 in the pH range 7.0–9.1, indicating that it is not hydroxyapatite which normally forms first in the physiological pH region. Characterization of the product by radio isotopes and by infrared spectroscopy and electron diffraction confirms the stoichiometry and indicates that the calcium phosphate nucleated from solution at high pH is an amorphous or soft metastable material. Some biological implications of these findings are pointed out.