Halogens have been coupled with metal anodes in a single cell to develop novel rechargeable batteries based on extrinsic redox reactions. Since the commercial introduction of lithium-iodine batteries in 1972, they have shown great potential to match the high-rate performance, large energy density, and good safety of advanced batteries. With the development of metal anodes (e.g. Li, Zn), one of the actual challenges lies in the preparation of electrochemically active and reliable iodine-based cathodes to prevent self-discharge and capacity decay of the rechargeable batteries. Understanding the fundamental reactions of iodine/polyiodide and their underlying mechanisms is still highly desirable to promote the rational design of advanced cathodes for high-performance rechargeable batteries. In this Minireview, recent advances in the development of iodine-based cathodes to fabricate rechargeable batteries are summarized, with a special focus on the basic principles of iodine redox chemistry to correlate with structure-function relationships.