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The effect of Cu(0) wire dimensions on the Cu(0) wire/Me₆-TREN-catalyzed heterogeneous single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA) initiated with methyl 2-bromopropionate (MBP) in DMSO at 25 °C was analyzed by kinetic experiments. These kinetic results were compared with those of Cu(0) powder/Me₆-TREN-catalyzed SET-LRP. Both wire and powder produce perfect SET-LRP with a first-order rate of polymerization in growing species up to 100% conversion. Nevertheless, Cu(0) wire experiments demonstrated SET-LRP with greater perfection, allowing for the accurate determination of the external rate order (vis-à-vis surface area) for heterogeneous Cu(0) catalyst and accurate prediction of k_p^app from wire dimension. Cu(0) wire also exhibited a significantly greater control of molecular weight distribution than Cu(0) powder. The combined advantages of easier …