Applying microbial electrolysis cells (MEC) is a biological approach to enhance the growth of high amounts of electroactive biofilm for extracellular electron transfer. The electroactive biofilm degrades the organics by oxidizing them at the anode and producing electrical energy. Addition of waste-activated sludge (WAS) with fat grease oil (FOG) produces an optimal reactor environment for microbial growth to enhance the exchange of electrons between cells via microbial electrolysis. The present work aimed to investigate the microbial approach to increase the extracellular electron transfer (EET) in microbial electrolysis cells. Results revealed that metabolites in electroactive microbes (EAM) grow viable cells that initiate high EET at anode sites. At optimum WAS with FOG addition, volatile fatty acid and current generation yield production was 2.94 ± 0.19 g/L and 17.91 ± 7.23 mA, accompanied by COD removal efficiency of 89.5 ± 14.4%, respectively. This study introduces a novel approach to anode biofilm engineering that significantly enhances extracellular electron transfer, offering a fresh perspective on bioenergy production. Our approach, which demonstrates that anodic biofilm enhances intercellular electron transfer, increases NADH-NAD ratio, and increases metabolite yield-fluxes, has the potential to revolutionize bio-electricity production. Results indicated that the electrolysis highlights MEC performance in power generation of 788 mV with 200 mL of anode volume of active viable cells by utilizing WAS with 11% FOG. The achievements of this study provide critical parameters for the anode biofilm engineering, demonstrating how growth cell volume, intercellular electron transfer, and increases in NADH-NAD ratio are evidence of an increase in the EET, compelling evidence for the resilience treatment and efficient current production. These findings are significant in advancing our understanding of bioenergy production.