A novel photobioelectrochemical system (PBES) was developed by acclimating algal-bacterial biofilm in both anode and cathode using Chlorella vulgaris and indigenous wastewater bacteria as inoculums. The PBES was operated in polarity reversion mode depend on dark/light alternate reaction to achieve simultaneous pH self-neutralization, azo dye degradation (Congo red) and bioelectricity generation. The anodic accumulated acidity and cathodic accumulated alkalinity were self-neutralized after polarity reversion and hence eliminate the membrane pH gradient. The Congo red was first decolored in the dark anode and the resultant decolorization liquid was subsequently mineralized after the dark anode changing to the photo-biocathode. The presence of C. vulgaris significantly enhanced the two-stage degradation of Congo red, with 93% increases in decolorization rates and 8% increases in mineralization compared to the algae-free BES. The PBES continuously generated stable voltage output over four months under repeatedly reversion of polarity. The maximum power density produced before and after polarity reversion was 78 and 61 mW/m(2), respectively. The synergy between C. vulgaris and mixed bacteria was responsible for the successful operation of the PBES which can be potentially applied to treat wastewater containing azo dye with benefits of enhanced azo dye degradation, high net power output and buffer minimization. (C) 2015 Elsevier B.V. All rights reserved.