This study investigates the effects of anodic pH on electricity generation in microbial fuel cells (MFCs) and the intrinsic reasons behind them. In a two-chamber MFC, the maximum power density is 1170 +/- 58 mW m(-2) at pH 9.0, which is 29% and 89% higher than those working at pH 7.0 and 5.0, respectively. Electrochemical measurements reveal that pH affects the electron transfer kinetics of anodic biofilms. The apparent electron transfer rate constant (k(app)) and exchange current density (i(o)) are greater whereas the charge transfer resistance (R(ct)) is smaller at pH 9.0 than at other conditions. Scanning electron microscopy verifies that alkaline conditions benefit biofilm formation in MFCs. These results demonstrate that electrochemical interactions between bacteria and electrodes in MFCs are greatly enhanced under alkaline conditions, which can be one of the important reasons for the improved MFC output. (C) 2011 Elsevier Ltd. All rights reserved.