Microbial electrolysis cells (MECs) offers a sustainable route for hydrogen production by decarbonizing global energy demands via transformation of biogenic waste/wastewater. Leveraging microbial metabolism, MECs contribute to the waste-to-energy nexus. The efficiency of MECs is significantly influenced by selection of electrode materials such as platinum, nickel, and stainless steel, which enhance the performance through their high surface area, chemical resilience, and effective hydrogen evolution reaction. MECs have been shown to generate 853 H2/m³/d using graphite brush (anode) and Pt-loaded carbon cloth (cathode). MECs were upgraded to 1000 l, having 24 modules with 144 electrode pairs. Key features of cathode materials and its advancements used in MECs are discussed in this review.