In this work, a strategy for chemical synthesis of ascorbic acid functionalized polyacrylates (PAAA) was accomplished in a two-step process, first a reversible addition fragmentation chain-transfer (RAFT) polymerization on a benzyl-protected ascorbyl acrylate monomer, followed by a deprotection (debenzylation) reaction. The polymers were characterized by H-1 NMR, C-13 NMR and gel permeation chromatograph. The polymerization ability of redox pair including PAAA and H2O2 were conducted through the measurement of 2-hydroxyethyl acrylate (HEA) conversion against time via real-time FT-NIR. It was found that PAAA in the presence of H2O2, independent on itself chain length, exhibited much faster polymerization than small molecule ascorbic acid (smAA) as reductant at identical condition. Interestingly, when the concentration of ascorbate repeating unit was over some critical value, the polymerization kinetics of HEA could be tunable by simply adjusting the initial molar ratio of reductant to oxidant and environmental pH. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1999-2007, 2011