Microbial fuel cell (MFC) technology is utilized to treat hexavalent chromium (Cr(VI)) from wastewater and to generate electricity simultaneously. The Cr(VI) is bioelectrochemically reduced to non-toxic Cr(III) form in the presence of an organic electron donor in a dual-chambered MFC. The Cr(VI) as catholyte and artificial wastewater inoculated with anaerobic sludge as anolyte, Cr(VI) at 100 mg/L was completely removed within 48 h (initial pH value 2.0). The total amount of Cr recovered was 99.87% by the precipitation of Cr(III) on the surface of the cathode. In addition to that 78.4% of total organic carbon reduction was achieved at the anode chamber within 13 days of operation. Furthermore, the maximum power density of 767.01 mW/m2 (2.08 mA/m2) was achieved by MFCs at ambient conditions. The present work has successfully demonstrated the feasibility of using MFCs for simultaneous energy production from wastewater and reduction of toxic Cr(VI) to non-toxic Cr(III).