The integration of bifunctionally active sites of multielement random alloy catalysts with other metal oxide electrocatalysts is a promising strategy for efficient electrochemical reactions. In this study, a novel combination of virtual crystal approximation and hydrothermal synthesis was used to investigate the composition-dependent structure and electrical property in a Ag1−xNix catalyst. The combination showed that a hexagonal closed-packed structure of Ag1−xNix with a compositional ratio of 6:4 (Ag:Ni) had electrical conductivity of ∼2 × 107 S∙cm−1 and an ionization potential of − 5.4 eV. Furthermore, the bifunctional oxygen electrocatalytic efficiencies of Ag0.6Ni0.4 were improved by forming a heterointerface with the CoNb2O6 electrocatalyst, resulting in a discharge-charge voltage gap of 0.81 V over 587 h, peak power density of 178.9 mW∙cm−2, and specific capacity of 806.8 mA∙h∙g−1 in a zinc–air battery. This approach was applied to pouch-type zinc–air batteries, resulting in long-term stability of over 158.6 h at 10 mA∙cm−2.