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.