The high-quality Pt48Ag52 alloy nano-octahedra are synthesized via one-pot hydrothermal method. The catalytic growth of Ag(0) atoms on Pt nuclei and selective oxidative etching on the Ag(0) atoms contribute to the formation of alloy nano-octahedra. Pt48Ag52 alloy nano-octahedra show excellent electrocatalytic activity and durability for the methanol oxidation reaction (MOR).