Bioanodes formed at an optimal potential of 200. mV vs. SHE and biocathodes developed at -. 300. mV vs. SHE in bioelectrochemical cells (BECs) enhanced the subsequent performances of microbial fuel cells (MFCs) compared to the un-treated controls. While the startup times were reduced to 320. h (bioanodes) and 420-440. h (biocathodes), PCP degradation rates were improved by 28.5% (bioanodes) and 21.5% (biocathodes), and power production by 41.7% (bioanodes) and 44% (biocathodes). Accordingly, there were less accumulated products of PCP de-chlorination in the biocathodes whereas PCP in the bioanodes was more efficiently de-chlorinated, resulting in the formation of a new product of 3,4,5-trichlorophenol (24.3. ±. 2.2. μM at 96. h). Charges were diverted to more generation of electricity in the bioanodes at 200. mV while oxygen in the biocathodes at -. 300. mV acted as a primary electron acceptor. Dominant bacteria known as recalcitrant organic degraders and/or exoelectrogens/electrotrophs included Desulfovibrio carbinoliphilus and Dechlorospirillum sp. on the bioanodes at 200. mV, and Desulfovibrio marrakechensis, Comamonas testosteroni and Comamonas sp. on the biocathodes at -. 300. mV. These results demonstrated that an optimal potential was a feasible approach for developing both bioanodes and biocathodes for efficient PCP degradation and power generation from MFCs. © 2013 Elsevier B.V.