A new concept to modify and enhance properties of existed functional micelles through self-complementary interaction has been exploited. In this study, a practical approach to the living polymerization of functionalized monomer allows for incorporation of self-constituted multiple hydrogen bonded groups into micelles with a potential application of supramolecular drug-delivery systems. The resulting micelles have a very low critical micellization concentration with very high loading capacity (16%), which makes them extremely stable and efficient loading process. We observed that the incorporation of anticancer drug doxorubicin (Dox) affected the micellization process of micelles in aqueous solution and enabled fine-tuning of drug loading and release. Release studies in vitro have shown that the antitumor activity of the released doxorubicin (Dox) is assessed using the human hepatocyte cell line HepG2. Dox-loaded micelles have the dose-dependent cytotoxicity to kill cancer cells at the body temperature. In addition, Dox-loaded micelles can be efficiently endocytosed by cancer cells, which allows them to serve as suitable vehicles of anticancer drugs for delivering effective, tumor targeting and metastatic disease. This newly developed material may provide a potential route towards next-generation drug delivery vehicles.