AbstractElectrochemical ammonia synthesis (EAS) presents an attractive alternative to the Haber–Bosch process due to the benefits of energy saving, low carbon emission, environmental friendliness, and so on. However, the competing hydrogen evolution reaction (HER) severely limits the yield, selectivity, and current efficiency of NH₃. Although the accumulation and self‐aggregation of active hydrogen (H*) are the primary causes of the competing HER, it also serves as the critical active species and intermediate for the multistep hydrogenation and deoxygenation processes. Therefore, the sensible regulation of the H* generation and consumption are essential for enhancing EAS performance. And it is significant to thoroughly review the current strategies for H* control. Herein, a comprehensive introduction of H* to provide a fundamental understanding of its role in electrochemical reactions, including generation, conversion, identification, and quantification protocols is first proposed. In addition, the role and control strategies of H* in EAS are carefully summarized with a particular focus on regulating H* generation and consumption to enhance the activity, selectivity, and Faradaic efficiency. Finally, the remaining challenges and perspectives are discussed. This critical review is intended to offer a profound understanding of the regulation of H* in electrochemical reactions and the development of EAS technology.