Tungsten carbide (WC) and tungsten carbide on reduced graphene oxide (WC + rGO) nanolayers show outstanding performance as anode catalysts in microbial fuel cells for the simultaneous generation of power and treatment of wastewater. In this work, we synthesized these catalysts using simple and cost-effective urea glass route and reduction-carburization techniques. The pristine carbon felt (CF), WC/CF, and WC + rGO/CF anodes were characterized using several techniques and tested in a practical microbial fuel cell using industrial wastewater. We found that the unique features of WC/CF and WC + rGO/CF anodes, i.e., the surface area, biocompatibility, structure morphology, and catalytic activity, resulted in significant performance improvements. In particular, WC + rGO/CF exhibited a 4.4-, 7.6-, and 2.1-fold power density, current density, and coulombic efficiency, respectively, relative to the benchmark CF anode. This study confirms the potential use of WC + rGO/CF as a viable anode catalyst in microbial fuel cells on a larger scale.