The effect of ammonium on microbial fermentation was investigated to improve the efficiency of microbial electrochemical cells (MXC). Electron balances of anaerobic microbial cultures with varying ammonium concentrations (reported as g N-NH4+/L) were used to study the distribution of electrons from different fermentable substrates to acetate, propionate, and methane. Results showed that with a high ammonium concentration (between 2.25 to 3g N-NH4+/L) fewer electrons routed to methane during the fermentation of 300 me-eq./L of electron donors .The majority of electrons (~ 60-80%) in the serum bottles experiments were routed to acetate and propionate for all fermentable substrates with high ammonium concentration. While methane cannot be utilized by anode respiring bacteria (ARBs) to produce current, both acetate and propionate can, which could lead to higher Coulombic efficiencies in MXCs. Experiments in microbial electrolysis cells (MECs) with glucose, lactate, and ethanol were performed. MEC experiments showed low percentage of electrons to current (between 10-30 %), potentially due to low anode surface area (~ 3cm2) used during these experiments. Nevertheless, the fermentation process observed in the MECs was similar to serum bottles results which showed significant diversion of electrons to acetate and propionate (~ 80%) for a control concentration of 0.5 g N-NH4+/L .