Polyhydric alcohols have excellent humectant properties. Triol - glycerol and hexitol - sorbitol also exhibit resistances to bacterial action and are important ingredients in dental products. Objective: To study the effect of these additives on the formation, growth and/or transformation of calcium phosphates (CaPs). Methods: The effect of glycerol and sorbitol was investigated in spontaneously precipitating systems and as the carriers for calcium and phosphate salts. CaP precipitation at 22 ºC was initiated by simultaneously mixing equal volumes of Ca- and PO4- reactant solution without or with glycerol and/or sorbitol. The polyalcohols were added to both Ca (≥11mmol/L) and PO4 (≥ 370mmol/L) reactants at the mass fractions of 14 to 45 %. Precipitation kinetics were followed by the changes in solution pH, calcium, fluoride and phosphate concentration. Solid phase(s) were isolated at different time intervals and identified by X-ray diffraction, FT-infrared spectroscopy and optical microscopy. Results: At high concentrations ((Ca+2)3(PO4-3)2≥ 10-21.2), amorphous calcium phosphate (ACP) formed initially in solution containing glycerol or sorbitol and then converted to apatites and/or dicalcium phosphate dihydrate depending on the pH of the solutions and the presence of fluoride. Glycerol and sorbitol decreased while fluoride and lower pH increased the hydrolysis rate of ACP to crystalline phases. The mixtures of soluble calcium and phosphate salts converted to calcium phosphates when in contact with water or humidity, yet were stable in the pure glycerol. Conclusion: These alcohols do not adversely affect the initial formation of ACP from solutions and calcium phosphates are less reactive in their presence. This is attributed to the lower dielectric constants of glycerol and sorbitol, resulting in decrease in solubility of calcium phosphates. Supported by ADAF and NIST.