The single-electron transfer living radical polymerization (SET-LRP) of vinyl chloride (VC) initiated with CHBr3 in dimethylsulfoxide (DMSO) at 25 degrees C was investigated using Cu(0) powder and Cu(0) wire as the catalyst. It was determined that living kinetics and high conversion are achieved only through the proper calibration of the ratio between Cu(0) and TREN and the concentration of VC in DMSO. For both Cu(0) powder and Cu(0) wire, optimum conversion was achieved with higher levels of TREN than reported in earlier preliminary reports and under more dilute conditions. Using these conditions, 85+% conversion of VC could be achieved with Cu(0) powder and wire to produce white poly(vinyl chloride) (PVC) with M-n = 20,000 and M-w/M-n = 1.4-1.6 in 360 min. The use of Cu(0) wire provides the most effective catalytic system for the LRP of PVC allowing for simple removal and recycling of the catalyst. In the Cu(0) wire-catalyzed SET-LRP of VC, the consumption of Cu(0) was monitored as a function of conversion. From these studies, it is evident that the catalyst can be recycled extensively before significant exchange of Cu(0) into Cu(II)X-2 and change in catalyst surface area is observed. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 164-172, 2010