This article highlights progress over the past decade in research on the preparation of controlled macromolecular architectures by means of sequential condensation and reversible-deactivation radical polymerizations. Such a dual approach for macromolecular engineering has become a subfield in itself over the years and is of great challenge for the development of advanced functional materials for targeted applications. Provided that conditions for adequate transformation chemistries and subsequent controlled polymerizations could be identified, physicochemical, mechanical, thermal and electrical properties of these complex macromolecules can be finely tuned by choosing and controlling the nature and length of the different polymer sequences together with molecular weight, composition and architecture of the copolymer. (C) 2012 Elsevier Ltd. All rights reserved.