The interactions of As(III) ion with C 2 H 5 OCS − 2 and C 2 H 5 SCS − 2 , known as the most popular collector ions, were studied by density functional theory (DFT) at the B3LYP/6-31G** level in connection with the arsenic-containing minerals realgar, orpiment, and arsenopyrite. The dixanthogen formations of these ions were also investigated at the same level of theory. The central purpose of this paper is to compare the stabilities of the major flotation products, namely As(III) xanthates and dixanthogens. The results show that the magnitudes of the interaction energies for the formations of As(III) xanthates and dixanthogens increase when the oxygen atom is replaced by the sulfur atom in C 2 H 5 OCS − 2 . Therefore, the C 2 H 5 OCS − 2 ion is preferred in these formations. The results obtained are in agreement with the experimental data reported.