The article discusses the challenges in electrochemical synthesis due to the scaling relationship among adsorption energies of different intermediates on electrocatalyst surfaces, impacting the design of efficient catalysts for multistep transformations. High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their multicomponent surface and diverse active sites. However, the vastness of HEA compositions and the convergence of adsorption energies pose obstacles. To tackle this, a 'surface entropy reduction' approach was developed to break the scaling relationship by exsolving few-atom-layer silver (FL-Ag) on the HEA surface. This novel catalyst design showed exceptional performance in converting nitrate to ammonia with high efficiency and stability, surpassing conventional HEAs. Through calculation-assisted designs, the article emphasizes the importance of providing varied adsorption energies, optimizing energy barriers, and balancing reactions for improved electrocatalyst performance. Experimental and simulation results validate the effectiveness of the FL-Ag/HEA catalyst in enhancing the complex electrochemical reactions, offering a new perspective on improving sustainable ammonia production through innovative catalyst design.