The development of bioactive materials with controllable preparation is of great significance for biomedical engineering. Citric acid-based biomaterials are one of the few bioactive materials with many advantages such as simple synthesis, controllable structure, biocompatibility, biomimetic viscoelastic mechanical behavior, controllable biodegradability, and further functionalization. In this paper, we review the development of multifunctional citrate-based biomaterials for biomedical applications, and summarize their multifunctional properties in terms of physical, chemical, and biological aspects, and finally the applications of citrate-based biomaterials in biomedical engineering, including bone tissue engineering, skin tissue engineering, drug/cell delivery, vascular and neural tissue engineering, and bioimaging.