Random and alternating copolymerizations of acrylates, methacrylates, acrylonitorile, and acrylamides with vinyl ethers under organotellurium-, organostibine-, and organobismuthine-mediated living radical polymerization (TERP, SBRP, and BIRP, respectively) have been studied. Structurally well-controlled random and alternating copolymers with controlled molecular weights and polydispersities were synthesized. The highly alternating copolymerization occurred in a combination of acrylates and vinyl ethers and acrylonitorile and vinyl ethers by using excess amount of vinyl ethers over acrylates and acrylonitorile. On the contrary, alternating copolymerization did not occur in a combination of acrylamides and vinyl ethers even excess amount of vinyl ethers were used. The reactivity of polymer-end radicals to a vinyl ether was estimated by the theoretical calculations, and it was suggested that the energy level of singly occupied molecular orbital (SOMO) of polymer-end radical species determined the reactivity. By combining living random and alternating copolymerization with living radical or living cationic polymerization, new block copolymers, such as (PBA-alt-PIBVE)-block-(PtBA-co-PIBVE), PBA-block-(PBA-alt-PIBVE), and (PTFEA-alt-PIBVE)-block-PIBVE, with controlled macromolecular structures were successfully synthesized. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 2254-2264, 2012