The present study investigated how polyols (sugar alcohols) affect the formation of calcium fluoride (CaF2) in the presence of fluoride 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 fluoride at room temperature to analyze CaF2 formation on the surfaces. Only glycerol enhanced fluoride incorporation significantly 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-containingCaF2 deposition, which can potentially prevent dental caries through the enhanced remineralization of enamel surfaces. Thus, fluoride may be involved in controlling the entire process of CaF2 deposition, dissolution, and remineralization of enamel.