In this paper, Cr oxygenated species dispersed on Pt nanowire assemblies (PtCrO_X NWs) were successfully prepared for the methanol oxidation reaction by a metal precursor dilution strategy. Notably, the PtCrO_X NWs catalyst exhibits excellent performance for electrocatalytic methanol oxidation. Density functional theory results revealed that the doped Cr oxygenated species, which moderated the electronic structure of the Pt atoms, can significantly decrease the free energy of COOH* formation, thus leading to superior methanol oxidation performance.