We have demonstrated Ag₃PO₄ as an active non-Pt electrocatalyst with enhanced activity compared with Ag for oxygen reduction reaction (ORR). Density functional theory reveals that better ORR performance of Ag atoms on Ag₃PO₄ surface than that on pure silver surface originates from more appropriate oxygen adsorption on positively charged Ag atoms. Further study of the surface geometry of Ag₃PO₄ including tetrahedron, rhombic dodecahedron and cube indicates that the highest density of Ag and appropriate oxygen adsorption on {110} surface of rhombic dodecahedral Ag₃PO₄ lead to the highest ORR activity, which is about 12 times that of Pt catalysts from a commercial perspective. It may be applicable for developing low-cost and highly active non-Pt catalytic materials from a broader range of material systems.