The production of large amounts of uranium-containing wastewater and its potential hazards has stimulated green and efficient material removal of uranium (VI). Inspired by the natural mineralization of bone, a facile and eco-friendly biomimetic synthesis of nano-hydroxyapatite (HAP) was carried out using chitosan (CS) as a template. It was found that the reaction temperature and the amount of precursors influence the particle size, crystallinity and specific surface area of the CS/HAP nanorods, and consequently their U(VI) adsorption efficiency. Moreover, the synthesized CS/HAP-40 with smaller particle size, lower crystallinity, and larger specific surface area show a more efficient U(VI) removal compared with CS/HAP-55 and CS/HAP-55-AT. It has a maximum adsorption capacity of 294.12 mg·g of the CS/HAP-40. Interestingly, the U(VI) removal mechanism of CS/HAP-40 in acidic (pH = 3) and alkaline (pH = 8) aqueous solutions was found to be different. As one of the main results, the U(VI) adsorption mechanisms at pH 8 could be surface complexation and ion exchange. On the contrary, three different mechanisms could be observed at pH 3: dissolution-precipitation to form chernikovite, surface complexation, and ion exchange.