Abstract A crucial issue restricting the application of direct alcohol fuel cells (DAFCs) is the low activity of Pt‐based electrocatalysts for alcohol oxidation reaction caused by the reaction intermediate (CO*) poisoning. Herein, a new strategy is demonstrated for making a class of sub‐monolayer YO x /MoO x ‐surface co‐decorated ultrathin platinum nanowires (YO x /MoO x –Pt NWs) to effectively eliminate the CO poisoning for enhancing methanol oxidation electrocatalysis. By adjusting the amounts of YO x and MoO x decorated on the surface of ultrathin Pt NWs, the optimized 22% YO x /MoO x –Pt NWs achieve a high specific activity of 3.35 mA cm −2 and a mass activity of 2.10 A mg Pt −1 , as well as the enhanced stability. In situ Fourier transform infrared (FTIR) spectroscopy and CO stripping studies confirm the contribution of YO x and MoO x to anti‐CO poisoning ability of the NWs. Density functional theory (DFT) calculations further reveal that the surface Y and Mo atoms with oxidation states allow COOH* to bind the surface through both the carbon and oxygen atoms, which can lower the free energy barriers for the oxidation of CO* into COOH*. The optimal NWs also show the superior activities toward the electro‐oxidation of ethanol, ethylene glycol, and glycerol.