Setting a biocathode potential at ?300 mV improved the subsequent performance of an MFC for Cr(VI) reduction compared to a control (no set potential). With this set potential, the startup time was reduced to 19 days, the reduction of Cr(VI) was improved to 19.7 mg/L d, and the maximum power density was increased to 6.4 W/m3 compared to the control (26 days, 14.0 mg/L d and 4.1 W/m3). Set potentials of ?150 mV and ?300 mV also improved system performance and led to similarly higher utilization of metabolic energy gained (PMEG) than set potentials of +200 mV and ?450 mV. We observed putative pili at ?150 and ?300 mV potentials, and aggregated precipitates on bacterial surfaces in both poised and nonpoised controls. These tests show that there are optimal potentials that can be set for developing a Cr(VI) biocathode. © 2011 American Chemical Society.