High‐entropy alloys (HEAs) are a promising group of materials composed of multiple elements (≥5) in nearly equal proportions (5 at%–35 at%), which exhibit uniformly mixed compositions and highly stable crystal structures and offer a wide range of design possibilities, making them exceptionally stable, multifunctional, and suitable for various applications. Recent research studies have identified the potential of HEAs as catalysts for electrocatalytic reactions, focusing on adjustable stress environments, optimizable d‐band centers, and high conformational entropy. Understanding the interactions among constituent elements, alloy formation, and catalytic reaction mechanisms is essential for optimizing HEAs' catalytic performance. This comprehensive review delves into the historical context, defining characteristics, and underlying significance of HEAs development. It also examines four primary effects of HEAs (high‐entropy effect, lattice distortion, sluggish diffusion, and cocktail effect) and their relevance to catalyst design criteria (selectivity, activity, stability, and cost). Additionally, it summarizes recent advances in nanostructured HEA catalyst synthesis, highlighting their advantages and challenges and explores the use of HEAs in electrocatalytic redox reactions involving small molecules (H, C, O, N). The paper underscores the importance of integrating experimental methods and theoretical calculations to design, synthesize, and understand alloy–property relationships of HEAs, emphasizing their vast potential for catalytic applications.