Bioelectrochemical system (BES) is a novel, self-sustaining metal removal technology functioning on the utilization of chemical energy of organic matter with the help of microorganisms. Experimental trials of two chambered BES reactor were conducted with varying substrate concentration using sodium acetate (500 mg/L to 2000 mg/L COD) and different initial chromium concentration (Cr-i) (10-100 mg/L) at different cathode pH (pH 1-7). In the current study mathematical models based on multiple linear regression (MLR) and non-linear regression (NLR) approach were developed using laboratory experimental data for determining chromium removal efficiency (CRE) in the cathode chamber of BES. Substrate concentration, rate of substrate consumption, Cr-i, pH, temperature and hydraulic retention time (HRT) were the operating process parameters of the reactor considered for development of the proposed models. MLR showed a better correlation coefficient (0.972) as compared to NLR (0.952). Validation of the models using t-test analysis revealed unbiasedness of both the models, with t critical value (2.04) greater than t-calculated values for MLR (-0.708) and NLR (-0.86). The root-mean-square error (RMSE) for MLR and NLR were 5.06 % and 7.45 %, respectively. Comparison between both models suggested MLR to be best suited model for predicting the chromium removal behavior using the BES technology to specify a set of operating conditions for BES. Modelling the behavior of CRE will be helpful for scale up of BES technology at industrial level. (C) 2018, The Society for Biotechnology, Japan. All rights reserved.