Zinc–cerium redox flow batteries (ZCBs) are emerging as a very promising new technology with the potential to store a large amount of energy economically and efficiently, thanking to its highest thermodynamic open-circuit cell voltage among all the currently studied aqueous redox flow batteries. However, there are numerous scientific and technical challenges that must be overcome if this alluring promise is to turn into reality, from designing the battery structure, to optimizing the electrolyte compositions and elucidating the complex chemical reactions that occur during charge and discharge. This review article is the first summary of the most significant developments and challenges of cerium half-cell and the current understanding of their chemistry. We are certain that this review will be of great interest to audience over a broad range, especially in fields of energy storage, electrochemistry, and chemical engineering.