In this study, the optimization of working cathode position in sleeve-type bioelectrochemical system (BES) was evaluated with inner/outer chamber for azo dye decolorization. Results showed that the working position in outer chamber performed better with decolorization efficiencies of 97.8 +/- 2.1% (7 h) and 94.0 +/- 2.3% (16 h) than that in inner chamber as the volume ratio V-cathode:V-anode = 1:1 and 3:1, respectively. The current and electrochemical impedance spectroscopy (EIS) analysis indicated that the proton/electron transfer and anolyte diffusion could be improved using outer chamber as working position. The decolorization with increased volume ratio could be further improved through the strategy of increasing substrate concentration, which would provide enough electrons and decrease diffusion resistance, further improving the whole performance with increased outer cathode volume. It has the great potential in sleeve-type configuration application and would create more challenges for process optimization and maintenance. (C) 2015 Elsevier Ltd. All rights reserved.