Copper(0) mediated radical polymerization is an efficient and versatile polymerization technique which allows the control of acrylates and methacrylates with an unprecedented maintenance of end group fidelity (similar to 100%) during the polymerization. In this highlight, we summarize recent works using Cu(0)-mediated radical polymerization for the synthesis of multiblock copolymers via an iterative approach. This approach has been successfully implemented for the synthesis of decablock copolymers, constituted of blocks with a degree of polymerization ranging from 3-4 to 100 units as well as for the preparation of multiblock star polymers. (C) 2014 Wiley Periodicals, Inc.