The distribution behavior of VA minor elements (As, Sb and Bi) in the smelting stage of the Mitsubishi process were evaluated thermodynamically based on thermodynamic data and operating data. The fractional distributions between the gas, slag and matte phases considered as the degree of vapor saturation of 1.0 are as follows: 53.8, 27.2 and 19% for As, 23.6, 56.6 and 19.8% for Sb, and 91.3, 1.1 and 7.6% for Bi, respectively. Arsenic is mostly distributed to the gas and slag phases. It is effectively eliminated by volatilizing and slagging. Antimony is mainly in the slag phase, which is suitably removed by slagging. Bismuth is easily vaporized to gas phase. The degree of vapor saturation has a large effect on the distribution behaviors of the three elements between the three phases. The amount of a minor element in the charge has an effect on the distribution of As but no effect on the distributions of Sb and Bi. Increasing matte grade and temperature results in the change of distributions for As and Sb, significantly. The change in the distribution ratio between slag and matte phases also considerably affects the distributions of As and Sb. The distribution behavior of Bi is not significantly changed by the change in matte grade, temperature and distribution ratio.