The reactivity of an enargite mineral electrode was investigated spectroelectrochemically under conditions typically found in alkaline sulfide leach solutions, with pH 11–13 and Na2S additions of 50 and 250 gL−1. A bulk enargite electrode was cycled between 0 and −1,000 mV for each set of solution conditions. Raman spectroscopy was used to determine and compare surface formations against species in mass-balanced EH-pH diagrams generated using STABCAL. Previously, it was determined that arsenic could be selectively leached under alkaline conditions at an average solution potential of −300mV, across the pH range 11–13. Operating under such conditions allowed for the selective leaching of arsenic with elemental sulfur formation. From several of the voltammograms obtained during this current testing, the formation of elemental sulfur appeared at increasingly reducing conditions with increasing sulfide concentration. At high concentrations, copper started to dissolve, possibly as a bisulfide complex, reducing the selectivity of the leach, unlike previous studies. However, the presence of the higher sulfide concentration is also anticipated to prevent passivation by consuming any surface formation of elemental sulfur. This study provides insight into the operating parameters of alkaline sulfide leaching in regards to the selectivity of arsenic leaching, as well as guidance for control of reagents and solution potential and, of course, the need for water treatment afterwards.