The behavior of minor elements in the smelting of copper concentrates has been of primary interest to those engaged in the design and evaluation of new smelting processes. As a contribution to that effort, the present study was undertaken to evaluate the behavior of bismuth in molten copper and copper-iron alloys. A re-evaluation of the data in the literature suggests that the first-order binary interaction parameter, for bismuth dissolved in molten copper is -2.5 at 1373K. This result was used to evaluate the first-order ternary interaction parameter for iron, giving a value of 40 at 1398K.