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Fluoride-substituted hydroxyapatite (FHAp) with high thermal and morphologic stability was successfully prepared by a molten salt synthesis route. XRD patterns and FTIR spectra identified the synthesized powders as FHAp solid solution. The FHAp obtained with potassium sulfate as the flux showed the rod-like morphology without detectable decomposition up to 1300°C and the flux, sodium sulfate, led to the spheriodal FHAp. After investigating the effects of salt species on the FHAp morphologies, it was found that solubility was not the exclusive factor, which affected the morphological development of apatite powders, and the cations of molten salt species also played an important role.