AbstractStar-shaped glycopolymers due to the attractive combination of the physicochemical, morphological, self-assembly properties along with biological activity have gained increased attention as innovative agents in novel cancer therapies. Unfortunately, the production of these highly desirable biomaterials remains a challenge in modern macromolecular chemistry. The main reason for that is the low polymerizability of ionic glycomonomers originated from their steric congestion and the occurrence of ionic interactions that generally negatively influence the polymerization progress and hinder controllable reaction pathway. In this work, the new ionic sugar monomer was (co)polymerized for the first time via Activator Generated by Electron Transfer Atom Transfer Radical Polymerization (AGET ATRP) using a three-arm resveratrol-based core to obtain star-like (co)polymers. The obtained products were examined in terms of their physicochemical properties and morphology. Aside from the synthesis of these new glycopolymers, also a thorough description of their thermal properties, ability to self-assembly, the formation of stable superstructures was studied in detail. It was found that examined (co)polymers did not show any heterogeneities and phase separation, while their variation of glass transition temperature (T_g) was strictly related to the change in the number of glycomonomer. Also, the stability and shapes of formed superstructures strictly depend on their composition and topology. Finally, we have shown that synthesized carbohydrate-based polymers revealed high antiproliferative activity against several cancer cell lines (i.e., breast, colon, glioma, and lung cancer). The cytotoxic activity was particularly observed for star-shaped polymers that were systematically enhanced with the growing concentration of amine moieties and molecular weight. The results presented herein suggest that synthesized star-shaped glyco(co)polymers are promising as drug or gene carriers in anticancer therapies or anti-tumor agents, depending on their cytotoxicity. Graphical abstract