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The elegance of the technique of ionic polymerization is the ability to synthesize polymers with well defined architectures without any side reactions. As the control of the polymerization becomes the motivation, atom-transfer radical polymerization, which has similar attributes of ionic polymerization and is a more recent addition to the armory of synthetic methods available to polymer chemists, was also included in the Symposium. Selected contributions presented at the Symposium have been compiled in this special volume of Macromolecular Symposia and is reflective of contemporary developments in the area of ionic polymerizations.