Elemental silver was used as a reducing agent in the atom transfer radical polymerization (ATRP) of acrylates. Silver wire, in conjunction with a CuBr2/TPMA catalyst, enabled the controlled, rapid preparation of polyacrylates with dispersity values down to (D) over bar = 1.03. The silver wire in these reactions was reused several times in sequential reactions without a decline in performance, and the amount of copper catalyst used was reduced to 10 ppm without a large decrease in control. A poly(n-butyl acrylate)-block-poly(tert-butyl acrylate) diblock copolymer was synthesized with a molecular weight of 91 400 and (D) over bar = 1.04, demonstrating good retention of chain-end functionality and a high degree of livingness in this ATRP system.