This study reports the fabrication of a new cathode electrode assembly using polyaniline (PANI) and graphene on a stainless steel mesh (SSM) as an alternative for the conventional expensive cathode of microbial electrolysis cells (MECs). With respect to the previous efforts to propose an efficient and cost-effective alternative for platinum (Pt) catalysts and cathode electrodes, the present study investigates the assessment of different catalysts to elucidate the potential of the modified SSM cathode electrode for larger-scale MECs. In the case of feeding dairy wastewater to the MEC, the maximum hydrogen production rate and COD removal were obtained by SSM/PANI/graphene cathode and had the values 0.805 m H m anolyte day and 82%, respectively, at the applied potential of 1 V. These values were only 20% and 7% lower than those of the MEC with Pt on the carbon cloth cathode, respectively. The coulombic efficiencies of SSM/Pt and SSM/PANI/graphene were seen to be 64.48% and 56.67%, respectively. It was also concluded that the fabrication cost of the modified cathode was 50% lower than the conventional cathodes with Pt on the carbon cloth. Finally, the evaluation of the modified cathode performance was achieved based on Fourier transform infrared spectroscopy, linear sweep voltammetry, scanning electron microscopy, and atomic force microscopy.