The present study investigated how polyols (sugar alcohols) affect the formation of calcium fluoride (CaF 2 ) in the presence of fl uoride on synthetic hydroxyapatite (HA) as a model of tooth enamel. HA plates were immersed in sugar alcohol solutions containing 10-60 (w/w)% xylitol, D-sorbitol, or glycerol and 1000 ppm fl uoride at room temperature to analyze CaF 2 formation on the surfaces. Only glycerol enhanced fl uoride incorporation signifi cantly and induced a nanoscale spherical deposition on the HA surface composed of calcium, fluoride, and a small amount of phosphorous according to energy-dispersive X-ray spectroscopic analysis. Overall results suggest that glycerol is capable of dissolving HA surfaces and enhancing phosphorous-containing CaF 2 deposition, which can potentially prevent dental caries through the enhanced remineralization of enamel surfaces. Thus, fl uoride may be involved in controlling the entire process of CaF 2 deposition, dissolution, and remineralization of enamel.