 The hydrogen evolution reaction, HER, is a half-cell reaction in water electrolysis for producing hydrogen gas. In industrial water electrolysis, the HER is often conducted in alkaline media to achieve higher stability of the electrode materials. However, the kinetics of the HER in alkaline medium is slow relative to that in acid because of the low concentration of protons in the former. Heterostructured catalysts with synergistic effects derived from their heterogeneous interfaces can provide multiple functional sites for the overall reaction process and have shown infusive potential to break through the bottlenecks. This review summarizes the most representative and recent heterostructured her catalysts for alkaline medium, focusing on approaches for enhancing the reaction rate by accelerating the Volmer step. This article was authored by Juming Wei, Min Zhou, An Chuan Long, and others.