A well-defined cyclobis(paraquat-p-phenylene) (CBPQT 4+ ) end-functionalized poly( n -butyl acrylate) 3 was prepared via RAFT polymerization using a new trithiocarbonate CBPQT 4+ derivative 2 as a reversible chain transfer agent. We have shown that the electron-poor CBPQT 4+ moiety at the α-chain-end could be specifically modified by complex formation with various functionalized macromolecules featuring complementary electron rich end groups, thereby leading to the corresponding supramolecular diblock copolymers. The latter could be conveniently disassembled upon heating, by applying electrochemical redox processes or by the addition of a competing molecular guest. Furthermore, we can generate new diblock architectures upon the addition of an appropriately functionalized polymer. We also describe preliminarily results regarding the formation of nanostructured architectures both in solution and in thin films.