Hydroxyapatite (HAP) is an easily synthesizable, low-cost mineral that has been recognized as a potential material for fluoride removal. Some of the synthesis methods of HAP are quite straightforward and cost-effective, while some require sophisticated synthesis techniques under advanced laboratory conditions. This review assesses the physicochemical characteristics of HAP and HAP-based composites produced via various techniques, their recent development in defluoridation and most importantly, the fluoride removal performances. For the first time, fluoride removal performances of HAP and HAP composites are compared based on partition coefficient (KD) instead of maximum adsorption capacity (Qmax), which is significantly influenced by initial loading concentrations. Novel HAP tailored composites exhibit comparatively high KD values indicating the excellent capability of fluoride removal along with specific surface areas above 120 m2/g. HAP doped with aluminium complexes, HAP doped ceramic beads, HAP-pectin nanocomposite and HAP-stilbite nanocomposite, HAP decorated nanotubes, nanowires and nanosheets demonstrated high Qmax and KD. The secret of HAP is not the excellent fluoride removal performances but best removal at neutral and near-neutral pH, which most of the defluoridation materials are incapable of, making them ideal adsorbents for drinking water treatment. Multiple mechanisms including physical surface adsorption, ion-exchange, and electrostatic interactions are the main mechanisms involved in defluoridation. Further research work must be focused on upscaling HAP-based composites for defluoridation on a commercial scale.