The Nernst-Monod model is used to describe bio-anode performance with respect to the effect of the electron donor and anode potential. However, electron competition is not considered in the model, limiting its application in wastewater treatment systems. In this work, nitrate was employed to describe the influence of a competitive electron acceptor on bio-anode performance. A new dynamic model of microbial anode respiration and nitrate respiration was developed for the removal of nitrogen oxides. The competitive relationship between microbial anode respiration and nitrate respiration was investigated based on electron transfer as described by the kinetics of Nernst-Monod electron transfer and nitrate reduction. The experimental results showed that nitrate had a significant influence on microbial anode respiration. The model parameters were estimated with the experimental results obtained in a continuous-flow bioelectrochemical system (BES) fed with acetate. The simulated results revealed that nitrate respiration could indirectly affect the microbial anode respiration by altering the available substrate concentration. In addition, bacterial community analysis indicated that there were two dominant functional microorganisms coexisting in the anode chamber. The first microorganism was represented by Geobacter, which has extracellular electron-transfer abilities. The second was denitrifying bacteria, which can use the carbon sources in the anodic chamber and electrons from the electrode for nitrate reduction. This is the first time that mathematical modelling of nitrate reduction has been applied to BESs.