It is generally accepted that ferric ions are effective for leaching chalcopyrite as an oxidant and ferrous ions contribute to the leaching only as a source of the oxidant ferric ions. However, this paper shows that ferrous ions are more useful for leaching chalcopyrite than oxidant ferric ions in sulfuric acid solutions in air at ambient temperatures. Leaching experiments and dissolved oxygen consumption measurements were carried out with a very pure chalcopyrite and 0.001 - 1 mol dm-3 sulfuric acid solutions containing 0 - 0.1 mol dm-3 ferric or ferrous ions at 303 K. Chalcopyrite oxidation with dissolved oxygen was promoted by ferrous ions but suppressed by ferric ions. As a result, the amount of extracted copper was larger with ferrous ions than with ferric ions. Effects of Thiobacillus ferrooxidans on the ferrous promoted chalcopyrite leaching were also investigated and discussed based on the experimental data.