This study investigates the relationship between the two main forms of Cu in wine and their impact on the rate of oxygen consumption. The Cu forms were differentiated by medium exchange constant current stripping potentiometry, which classified the Cu as either bound to sulfide or not. Oxygen consumption rates were determined in red, white and model wines after saturation with oxygen. The results for white wines showed that the oxygen consumption was sensitive to the non-sulfide-bound Cu concentration when ascorbic acid was present, and the first order rates ranged from 0.02 to 0.11 h−1. However, the same was not true for wines without added ascorbic acid that showed little influence of Cu form on oxygen decay rates. Cu forms were also found to significantly change in some wines during the oxygen decay experiment. Ascorbic acid is critical in enabling the form of Cu to significantly influence the oxygen reaction rate in wine.