The combined anaerobic-aerobic conditions in air-cathode single-chamber MFCs were used to completely mineralize pentachlorophenol (PCP; 5 mg/L), in the presence of acetate or glucose. Degradation rates of 0.140 ± 0.011 mg/L-h (acetate) and 0.117 ± 0.009 mg/L-h (glucose) were obtained with maximum power densities of 7.7 ± 1.1 W/m(3) (264 ± 39 W/m(2), acetate) and 5.1 ± 0.1 W/m(3) (175 ± 5 W/m(2), glucose). At a higher PCP concentration of 15 mg/L, PCP degradation rates increased to 0.171 ± 0.01 mg/L-h (acetate) and 0.159 ± 0.011 mg/L-h (glucose). However, power was inversely proportional to initial PCP concentration, with decreases of 0.255 W/mg PCP (acetate) and 0.184 W/mg PCP (glucose). High pH (9.0, acetate; 8.0, glucose) was beneficial to exoelectrogenic activities and power generation, whereas an acidic pH = 5.0 decreased power but increased PCP degradation rates (0.195 ± 0.002 mg/L-h, acetate; 0.173 ± 0.005 mg/L-h, glucose). Increasing temperature from 22 to 35°C enhanced power production by 37% (glucose) to 70% (acetate), and PCP degradation rates (0.188 ± 0.01 mg/L-h, acetate; 0.172 ± 0.009 mg/L-h, glucose). Dominant exoelectrogens of Pseudomonas (acetate) and Klebsiella (glucose) were identified in the biofilms. These results demonstrate that PCP degradation using air-cathode single-chamber MFCs may be a promising process for remediation of water contaminated with PCP as well as for power generation.