Homo and copolymers were synthesized from enantionpure (R)- and (S)-1-(4-vinylphenyl)ethanol by reversible addition-fragmentation chain transfer polymerization. The polymerization conditions were optimized resulting in dioxane as the preferred reaction solvent. First-order polymerization kinetics and well-defined enantiopure homopolymers with low dispersities were obtained. In agreement with their enantiomeric composition, the (R) and (S)-polymers gave opposite optical rotation of light. Polymer analogous esterification of the chiral hydroxy groups catalyzed by enantioselective Candida antarctica Lipase B was strongly (R)-selective. Esterification on the homopolymer and copolymers could be achieved to a maximum of around 50 %. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013