The concentration and variational trend of As3+ and As5+, the bacterial resistance for the As3+ and As5+ and converting conditions from As3+ to As5+ were analyzed. The additive was used to prompt the bacterial leaching efficiency by changing valence state of arsenic. The results show that the concentration of As3+ is larger than that of As5+ in the lag phase. The concentration of As3+ decreases in the log phase, and is lower than that of As5+. HQ-0211 typed bacteria express better resistance for As3+ and As5+ and remain growing when the concentrations of As3+ and As5+ are above 6.0 g/L and 12.0 g/L, respectively. It is found that Fe3+ cannot oxidize As3+ singly as strong oxidant in the leaching system, but can cooperate with pyrite or chalcopyrite to do that. The oxidation of As3+ is prompted with addition of H2O2. The bacterial activity is improved in favor of bacterial leaching efficiency. NaClO restrains the bacterial growth to depress leaching efficiency because of the chloric compounds affecting bacterial activity.