Large-area icosahedral-AB13-type Pt鈥揚d binary superlattices (BNSLs) are fabricated through self-assembly of 6 nm Pd nanocrystals (NCs) and 13 nm Pt octahedra at a liquid鈥揳ir interface. The Pt鈥揚d 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鈥揚d into a single crystalline nanostructure. The Pt鈥揚d BNSLs are promising catalysts for the oxygen electrode of fuel cells.