Postfunctionalization of high-molecular-weight syndiotactic polystyrene (sPS) was achieved via combination of electrophilic bromination at the para-position of the polymer aromatic ring and subsequent Suzuki-Miyaura cross-coupling reactions with functionalized phenylboronic acids. The concentration of brominated styrene repeating unit in sPS was conveniently controlled by changing the ratio of added bromine relative to the polymer repeating unit. Brominated sPS (8.5 mol %) was converted quantitatively to other polar functional groups via Suzuki-Miyaura cross-coupling reactions with various functional group-substituted phenylboronic acids. The surface properties of functionalized sPS were studied by measuring water contact angles. (c) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4335-4343, 2010