Abstract: Microbial electrolysis cells (MECs) present an attractive route for energy-saving hydrogen (H₂) production along with treatment of various wastewaters, which can convert organic matter into H₂ with the assistance of microbial electrocatalysis. However, the development of such renewable technologies for H₂ production still faces considerable challenges regarding how to enhance the H₂ production rate and to lower the energy and the system cost. In this review, we will focus on the recent research progress of MEC for H₂ production. First, we present a brief introduction of MEC technology and the operating mechanism for H₂ production. Then, the electrode materials including some typical electrocatalysts for hydrogen production are summarized and discussed. We also highlight how various substrates used in MEC affect the associated performance of hydrogen generation. Finally we presents several key scientific challenges and our perspectives on how to enhance the electrochemical performance.