This article describes the syntheses of various functional star-shaped polymers via monomer-selective living cationic polymerization of a vinyl ether (VE) and a divinyl compound with alkoxystyrene moieties by a one-shot method. An aqueous solution of the resulting star-shaped polymers with oxyethylene pendants exhibits thermally induced phase separation behavior. To achieve domino synthesis from various monomers, we investigated the optimum reactivity difference using a functional VE and a monofunctional alkoxystyrene. Moreover, the one-shot copolymerization of a bifunctional VE and an alkoxystyrene is also conducted to yield a star-shaped polymer via the core-first method. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019