A novel type of stimuli-responsive copolymer micelles based on supramolecularamphiphilic multiarm hyperbranched copolymer, Boltorn?H40-star-poly(ε-caprolactone)-adenine:uracil-poly(ethylene glycol)(H40-star-PCL-A:U-PEG), was prepared as a carrier for rapid intracellular release ofdrugs. The hydrophobic polyester core and hydrophilic PEG arms were linkedthrough molecular recognition of nucleobases. Benefiting from amphiphilic structure,H40-star-PCL-A:U-PEG was able to self-assemble into stable micelles in aqueoussolution. Moreover, the size of self-assembled micelles could be easily tailored bychanging the ratio of hydrophobic H40-star-PCL-A core and hydrophilic U-PEG arm.In vitro evaluation of these supramolecular micelles against NIH/3T3 normal cellsdemonstrated their low cytotoxicity by methyl tetrazolium (MTT) assay. As ahydrophobic anticancer model drug, doxorubicin (DOX) was encapsulated into thesesupramolecular micelles. Due to the dynamic and sensitive nature of non-covalentinteractions, the in vitro release of DOX from supramolecular micelles wassignificantly accelerated at an acid environment compared to physiological pH. MTTassay against Hela cancer cells showed that DOX-loaded micelles had high anticancerefficacy. Hence, these supramolecular multiarm hyperbranched copolymer micellesbased on the molecular recognition of nucleobases are promising candidates for rapidcontrolled release of drugs.