Miktoarm star copolymers, which are in the simplest form of branching, are particularly of interest to biomedical applications. Nevertheless, their synthesis is facing troubles of seeking inner cores with heterogeneous functional groups as well as tedious protection and deprotection. Herein, ethyl-beta-D-glucopyranoside, a sugar molecule containing homogeneous groups, was directly employed as a core to synthesize an amphiphilic miktoarm star copolymer via a chemoenzymatic approach without complicated decoration and protection of the core. Because of the high regioselectivity originated from enzymatic catalysis, the resultant copolymers with well-regulated molecular architecture were synthesized, which can self-assemble into highly-stable nanoaggregates in aqueous media. The copolymers were nontoxic in preliminary in vitro cytotoxicity assays and able to carry doxorubicin into tumor cells, indicating their promising application as a new biocompatible platform for drug delivery. (C) 2016 Elsevier Ltd. All rights reserved.