Abstract Nonmetal heteroatom incorporation into the lattice of host materials is a common way to regulate the surface electronic structure of electrocatalysts to boost their electrocatalytic performance. However, the heteroatom incorporation will inevitably trigger lattice strain and vacancy, which may lead to large changes in the structure of host materials. In this situation, the reconstruction of doped catalysts easily occurs during the catalytic process under harsh alkaline media, which hinders understanding the structure–activity correlation between catalysts and catalytic performance. Herein, taking cobalt nitride as an example, it is promulgated that a low‐temperature selenium sublimation strategy can effectively optimize the surface electronic structure in Co 4 N nanowire arrays with no significant change of bulk phase structure. Benefiting from surface selenium modification, the optimized SeCo 4 N nanowire arrays exhibit a 6.5 times enhancement of catalytic activity with structural phase stability for hydrogen evolution reaction in basic media. These findings may provide a new concept to design stable structured catalysts for energy‐related applications.