This paper focuses on the study of the effect of electrolysis on activated sludge in a microbial electrolysis cell (MEC) under the anaerobic digestion of poultry manure. This study was conducted using a bioreactor design with and without electrodes (conventional condition). Measurements of pH, redox potential (ORP), and total dissolved solids were carried out, as was the microscopy of activated sludge during treatment and gasometry. There was an increase in the yields of CH4 and CO2 compared to conventional conditions. Thus, on the 14th day, there was an increase in the CH4 yield to 35.1% compared with the conventional conditions—31.6%—as well as in the CO2 yield to 53.5% compared with the cell without electrodes—37.7%. Visually, the microscopy of anaerobic activated sludge showed changes in the aggregation process itself, with the formation of cells of clusters of microorganism colonies with branches of a delineated shape. ORP fluctuations were related to the process of the dissociation into ions during the passage of an electric current through the electrodes, and were observed before and after the inclusion of a current into the system. A model of the effect of electrolysis during anaerobic digestion was developed, taking into account the influencing factors on the condition of the activated sludge.