Halogen bonding (XB) has been used to catalyze organic reactions and polymerizations, which is an emerging research area. Reversible complexation mediated polymerization (RCMP) is an XB-catalyzed living radical polymerization and is one of the most promising examples of the XB catalysis. RCMP utilizes alkyl iodides as initiating dormant species and electro-donating molecules and ions such as amines, iodide anions, and oxyanions as catalysts. Various initiating dormant species and catalysts were developed, enabiling the synthesis of well-defined homopolymers and block copolymers with complex architectures, chain-end functionalization, photo-polymerization, and industrial application. The use of inexpensive non-metallic catalysts and the accessibility to a wide range of polymer structures are attractive features of RCMP. This mini-review summarizes the current research status of RCMP and its uniqueness brought via the XB catalysis.