Organotellurium-mediated living radical polymerizations (TERPs) and organostibine-mediated living radical polymerizations (SBRPs) provide well-defined polymers with a variety of polar functional groups via degenerative chain-transfer polymerization. The high controllability of these polymerizations can be attributed to the rapid degenerative-transfer process between the polymer-end radicals and corresponding dormant species. The versatility of the methods allows the synthesis of AB diblock, ABA triblock, and ABC triblock copolymers by the successive addition of different monomers. This review summarizes the current status of TERP and SBRP. (c) 2005 Wiley Periodicals, Inc.