Electrochemical nitrogen reduction reaction (eNRR) is promising in place of the Haber–Bosch process for artificial N2 fixation. However, the high activity and selectivity of eNRR are challenging to achieve simultaneously due to the scaling relations. Such “leverage” between activity and selectivity has severely restricted eNRR. To overcome this bottleneck, the complementary design of electronic structures in multicomponent electrocatalysts has been recently pursued, aiming to maximize the advantages of each component and optimize the multistep reactions, which has stood at the cutting edge in this aspect. Here, we present a minireview of the design, performance, and mechanism of multicomponent electrocatalysts with complementary electronic structures. We particularly emphasize the interactions between N2 and elements from d‐, p‐, and s‐blocks, which are essential for understanding how these electrocatalysts are beyond the “leverage” between activity and selectivity. By integrating distinct yet complementary electronic structures of elements in different blocks, this concept is revolutionary in that it breaks the limitations of scaling relations, synchronously achieving high activity and selectivity for electrochemical nitrogen reduction.