In this review article the available results about application of sol–gel synthesis method for the preparation of different calcium phosphates and composite materials are summarized. The attention is paid to calcium phosphate-containing compounds which show the biological properties and could be used as potential phosphate bioceramics in medicine. It was demonstrated that the sol–gel synthesis method is a powerful tool for the synthesis of calcium hydroxyapatite and other phosphates, and different calcium phosphate-based composites at mild synthetic conditions resulted in high reproducibility, high phase purity, and desired morphology. Thus, the sol–gel synthesis method enables the researchers to develop biomaterials with superior features in terms of biomedical applications. For the synthesis of calcium phosphate biomaterials an effective sol–gel chemistry approaches have been developed. KI, EG, and AK. “Sol–gel synthesis of calcium phosphate-based biomaterials—A review of environmentally benign, simple, and effective synthesis routes”. Highlights The sol-gel chemistry approaches for synthesis of calcium phosphate biomaterials were observed. Calcium hydroxyapatite, different calcium phosphates, and composites are discussed. These CP biomaterials show a high biocompatibility and increased biological behaviour. The sol-gel synthesis method is a powerful tool for the synthesis of CP biomaterials. High reproducibility, high phase purity and desired morphology could be achieved.