A biocompatible and novelly-defined adsorption membrane for rapid removal of fluoride was prepared. Both adsorption and membrane techniques were used in this research. Al(OH)3 nanoparticles modified hydroxyapatite (Al-HAP) nanowires were developed and made into Al-HAP membrane. The adsorption data of Al-HAP adsorbent could be well described by Freundlich isotherm model while the adsorption kinetic followed pseudo-second-order model. The maximum of adsorption capacity was 93.84 mg/g when the fluoride concentration was 200 mg/L. The adsorption mechanism was anion exchanges and electrostatic interactions. The contribution rates of HAP nanowires and Al(OH)3 nanoparticles in fluoride removal were 36.70% and 63.30%, respectively. The fixed-bed column test demonstrate that the Al-HAP was biocompatible and in a good stability during the process of water treatment. The fluoride removal abilities of Al-HAP membrane with 0.3 mm thickness could reach 1568 L/m2 when fluoride concentrations were 5 mg/L. This study indicated that the Al-HAP membrane could be developed into a very viable technology for highly effective removal of fluoride from drinking water.