The endeavor for utilization of various kinds of organic wastes into a valuable energy source through the process of anaerobic digestion is gaining ground amongst the researchers worldwide. In this context, a single chamber, above the ground, portable anaerobic digester (AD) was developed which was hybridized with a membrane electrode assembly (MEA) to facilitate the generation of enriched biogas and electricity as a byproduct. The analysis showed enrichment of CH4 in the biogas, while the AD was hybridized with the MEA. The highest concentration of CH4 in control was 56.3 ± 1.5% whereas in AD-MEA, the concentration of CH4 increased to 73.7 ± 3.9%. Thus, the incorporation of conductive surface in the anaerobic chamber of the AD-MEA system could promote the enrichment of methane. The presence of the non-biological conductive surface in the anaerobic chamber stimulated syntrophic interactions among exoelectrogens and hydrogenotrophic methanogens for conversion of CO2 directly to CH4. Moreover, the hybridized AD-MEA system could produce a maximum of 496 ± 7 mV OCV, with a maximum average power density of 2.87 mW/m2 and 70 mA/m2 current density.