Microbial fuel cell, as a promising technology, utilizes microorganisms to break down and oxidize the organic matter for harvesting energy. Progress in creating specific compositional functionalities of electrodes that are catalytically active, durable, cost-effective, and energy-recovery efficient is exclusively challenging for microbial fuel cell operation because of its bio-compatibility requirement. The electrodes composition impresses the oxidation-reduction reaction and electron charge-discharge rates. This study explores the use of silver/silver tungstate supported on different kinds of carbon materials, as cathode material for microbial fuel cells. The as-prepared catalysts were synthesized by a simple, environment-friendly, and self-developed surfactant-less method. Among proposed catalysts, the Ag/Ag2WO4@f-MWCNTs upgraded the oxygen reduction reaction to a four-electron pathway. As well, the optimal catalyst Ag/Ag2WO4@f-MWCNTs, exhibited excellent oxygen reduction reaction performance activity and stability with onset potential of -0.037 V and kinetic current density of 17.66 mA cm(-2) compared with other synthesized catalysts and even the standard Pt/C catalyst. Owing to the more active sites, larger surface, and faster charge transfer, the microbial fuel cell equipped Ag/Ag2WO4@f-MWCNTs device delivered a high power density and current density of 0.965 W m(-2) and 6.43 A/m(-2)(-vertical bar-), respectively. Consequently, Ag/Ag2WO4@f-MWCNTs is an effective catalyst that has the potential to be an alternative to Pt/C-based oxygen reduction reaction catalysts. The usage of this Ag/Ag2WO4@f-MWCNTs catalyst can therefore substantially improves power production and enable broader applications of microbial fuel cells for renewable electricity generation using waste materials.