Smart materials can respond to external physical or chemical stimuli in controlled conditions. Azo dyes are widely used in industry and medicine due to their physicochemical properties. The photoisomerization ability of azo compounds has made them attractive candidates for the design of compounds with photo-responsive properties and use in drug delivery. In this work, a light-sensitive polymer containing azobenzene as the core and hyperbranched polyglycerol as the shell (called AzoHPG) was synthesized via anionic ring-opening polymerization. The structure of Azo-HPG was analyzed by FT-IR, NMR, DLS, and GPC. The ability of polymer in the delivery of doxorubicin was investigated under UV irradiation and diferent pH conditions.