Abstract:World copper (Cu) production has been strongly affected by arsenic (As) content, because As-rich Cu concentrates are not desirable in the metal foundries. When As-rich Cu concentrates are processed by smelting they release As as volatile compounds into the atmosphere and inside furnaces, generating serious risks to human health. In recent years, exports of Cu concentrates are being penalized for the increasingly high As content of the ores, causing economies that depend on the Cu market to be seriously harmed by this impurity. In the last few decades, biohydrometallurgy has begun to replace the traditional Cu sulfide processing, however bioleaching processes for As-bearing Cu ores which contain enargite are still in the development stage. Researchers have not yet made successful progress in enargite bioleaching using typical mesophilic and thermophilic bacteria that oxidize sulfide. New approaches based on direct oxidative/reductive dissolution of As from enargite could result in significant contributions to Cu biohydrometallurgy. Thus, As-rich Cu concentrates could be pre-treated by bioleaching, replacing current technologies like roasting, pressure leaching and alkaline leaching by selective biological arsenite oxidation or arsenate reduction. In this article, we review the As problem in Cu mining, conventional technologies, the biohydrometallurgy approach, and As bioleaching as a treatment alternative.