Research interest in electrochemical redox stimulus has grown considerably due to its easy trigger mode, in which the linkers have played important roles, such as the beta-cyclodextrin-ferrocene (beta-CD-Fc) linker. Star amphiphilic copolymers with well-defined and flexible structures are considered to be excellent choices for drug delivery systems (DDSs). Driven by the idea that using star polymers to improve the biocompatibility and efficiency of the beta-CD-Fc-based DDS, we designed and synthesized star polymer 4 arm-poly(epsilon-caprolactone)-beta-CD (4A PCL-CD) and linear polymer polyethylene glycol-Fc (PEG-Fc). They can form supramolecular block copolymer 4A PCL-CD/Fc-PEG and self-assemble to micelles, which are electrochemical responsive and can be applied as drug carriers for potential controlled release, with higher efficiency and better biocompatibility compared with their linear analogues. (C) 2016 Elsevier Ltd. All rights reserved.