Calcium phosphates (CaPs) are ubiquitous in nature and vertebrate bones and teeth, and have high biocompatibility. The fabrication of CaPs with structures mimicking those of the bones and teeth has promising applications in clinic. The successful large-scale preparation of biomi-metic CaP, particularly hydroxyapatite (HAp), may lead to the improvement of properties and structural design of biomedical application mate-rials. Up to now, it is still difficult to synthesize bone-like and enamel-like CaP materials with highly oriented architectures. Recently, hydroxyapatite (HAp) crystals with hierarchical structures have made great progress in clinical repair of bones and teeth. A series of strategies have been used to synthesize bionic HAp structures. The design of CaP hierarchical organization, have great potential to revolutionize the field of hard tissue engineering. Previously, a number of reviews have reported the synthesis and properties of CaP materials. However, most of them mainly focused on the characterizations and physicochemical and biological properties of HAp particles, e. g. synthesis, characteristics, application, surface modification and control of shape and size of HAp particles. There were few reviews about the control of HAp crystal biomimetic arrays. The current state of the art for the synthesis of HAp crystals hierarchical organization were reviewed, including the molecule directing mineralization method, solution-induced calcium phosphate (CaP) formation method, hydrothermal/solvothermal method, precursor transformation methods, sol-gel methods and electrochemical deposition methods. In addition, advantages and disadvantages of these methods were discussed. Moreover, the possible directions of future research and development in this field were provided as references for the preparation of biomimetic HAp. © 2020, Materials Review Magazine. All right reserved.
