In this study, the performance of a three-chamber microbial desalination cell (MDC) was assessed to simultaneously remove salt (35 g.L-1) from water and degrade phenol as a hazardous compound. Two parallel MDCs with the same configurations were run using glucose as the chemical oxygen demand (COD) at an initial concentration of 1.5 g.L-1 as the anolyte. MDC#1 operated with 10 mM phosphate buffer solution (PBS), while MDC#2 operated with bio-cathode as the catholyte for the degradation of 100 mg.L-1 of phenol. The use of MDC#1 resulted in a power density, desalination efficiency, and COD removal of 366.2 mW.m−2, 50.3 ± 4.0 %, and 79.3 ± 2.2 %, respectively. All performance parameters were improved in MDC#2 with bio-cathode so that power density, desalination efficiency, and COD removal reached 660.1 mW.m−2, 72.1 ± 3.0 %, and 92.6 ± 2.4 %, respectively. Also, more than 96 % of phenol was degraded using bio-cathode within 7 h of operation. Bio-cathode could enhance the performance of the MDC reactor through catalyzing the final reactions of electron acceptors compared to MDC#1 with a chemical cathode. In general, the results indicated that heterotrophic microorganisms, able to grow alongside autotrophic bacteria, could effectively extend the applications of MDC reactors to degrade hazardous compounds in cathode chambers.