The dissolution of chalcopyrite in association with pyrite in mine waste results in the severe environmental issue of acid and metalliferous drainage (AMD). To better understand chalcopyrite dissolution, and the impact of chalcopyrite’s galvanic interaction with pyrite, chalcopyrite dissolution has been examined at 75 °C, pH 1.0, in the presence of quartz (as an inert mineral) and pyrite. The presence of pyrite increased the chalcopyrite dissolution rate by more than five times at Eh of 650 mV (SHE) (Cu recovery 2.5 cf. 12% over 132 days) due to galvanic interaction between chalcopyrite and pyrite. Dissolution of Cu and Fe was stoichiometric and no pyrite dissolved. Although the chalcopyrite dissolution rate at 750 mV (SHE) was approximately four-fold greater (Cu recovery of 45% within 132 days) as compared to at 650 mV in the presence of pyrite, the galvanic interaction between chalcopyrite and pyrite was negligible. Approximately all of the sulfur from the leached chalcopyrite was converted to S0 at 750 mV, regardless of the presence of pyrite. At this Eh approximately 60% of the sulfur associated with pyrite dissolution was oxidised to S0 and the remaining 40% was released in soluble forms, e.g., SO42−.