The synthesis of poly(tert-butyl acrylate-block-vinyl acetate) copolymers using a combination of two living radical polymerization techniques, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization, is reported. The use of two methods is due to the disparity in reactivity of the two monomers, viz. vinyl acetate is difficult to polymerize via ATRP, and a suitable RAFT agent that can control the polymerization of vinyl acetate is typically unable to control the polymerization of tert-butyl acrylate. Thus, ATRP was performed to make poly(tert-butyl acrylate) containing a bromine end group. This end group was subsequently substituted with a xanthate moiety. Various spectroscopic methods were used to confirm the substitution. The poly(tert-butyl acrylate) macro-RAFT agent was then used to produce (tert-butyl acrylate-block-vinyl acetate). (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7200-7206, 2008