Abstract Electrochemical transformation processes involving carbon, hydrogen, oxygen, nitrogen, and small‐molecule chemistries represent a promising means to store renewable energy sources in the form of chemical energy. However, their widespread deployment is hindered by a lack of efficient, selective, durable, and affordable electrocatalysts. Recently, grain boundary (GB) engineering as one category of defect engineering, has emerged as a viable and powerful pathway to achieve improved electrocatalytic performances. This review presents a timely and comprehensive overview of recent advances in GB engineering for efficient electrocatalysis. The beneficial effects of introducing GBs into electrocatalysts are discussed, followed by an overview of the synthesis and characterization of GB‐enriched electrocatalysts. Importantly, the latest developments in leveraging GB engineering for enhanced electrocatalysis are thoroughly examined, focusing on the electrochemical utilization cycles of carbon, hydrogen, oxygen, and nitrogen. Future research directions are proposed to further advance the understanding and application of GB engineering for improved electrocatalysis.
