Large-area icosahedral-AB(13)-type Pt-Pd binary superlattices (BNSLs) are fabricated through self-assembly of 6 nm Pd nanocrystals (NCs) and 13 nm Pt octahedra at a liquid air interface. The Pt-Pd BNSLs enable a high activity toward electrocatalysis of oxygen reduction reaction (ORR) by successfully exploiting the shape effects of Pt-NCs and synergistic effects of Pt-Pd into a single crystalline nanostructure. The Pt-Pd BNSLs are promising catalysts for the oxygen electrode of fuel cells.