Fluorosis is a major scourge in many countries caused by prolonged consumption of drinking water with high fluoride content found in groundwater resources. Hydroxyapatite (Hap) and its composite forms are excellent biomaterials that recently gained attention as efficient adsorbents, owing to its physical and chemical nature as it can substitute both cationic and anionic complexes present in an aqueous solution in its atomic arrangement. Its biological nature, biocompatibility and biodegradability along with its chemical characteristics such as crystallinity, stability, ion adsorption capability and highly specific catalytic activity make it suitable for a variety of applications especially in water treatment for fluoride removal. This review describes various techniques for synthesis of a wide variety of biogenic, synthetic, composite and modified forms of Hap for application in water defluoridation. Hap derived from natural sources or synthesized using conventional methods, hydrothermal, sol-gel or advanced sonication-cum-precipitation technique varied in terms of its crystallinity, structure, size, etc., which affect the fluoride removal capacity. The advantage and disadvantages of various synthesis methods, process parameters and product characteristics have been compiled, which may help to identify a suitable synthesis method for a desired Hap product for potential application and future perspectives in water treatment.