The mechanism by which pyrrhotite is depressed by diethylenetriamine (DETA) during pentlandite flotation has been studied. Amyl xanthate is observed to adsorb on pyrrhotite to form both dixanthogen and iron xanthate. In the presence of DETA, the amount of xanthate adsorbed on pyrrhotite is substantially reduced as evidenced by infrared and UV/Vis spectroscopy. However, DETA does not adsorb on pyrrhotite as evidenced by infrared and X-ray photoelectron spectroscopy. DETA shifts the potential of the onset of xanthate adsorption on pyrrhotite by approximately 200 mV toward anodic direction, which is thought to be due to the increased solubility of surface oxidized species on pyrrhotite in the presence of DETA. A window of selectivity for the separation of pentlandite and pyrrhotite is provided by the results obtained in this study.