Hollow Pt-based nanowires (NWs) have important applications in catalysis. Their preparation often involves a two-step process in which M (M=Ag, Pd, Co, Ni) NWs are prepared and subsequently subjected to galvanic reaction in solution containing a Pt precursor. It is challenging to achieve a simple one-step preparation, because the redox potential of Pt /Pt or Pt /Pt to Pt is high, and therefore, Pt atoms always form first. This work demonstrates that an appropriate pH can decrease the redox potential of Pt /Pt and allows the one-step preparation of high-quality hollow Pt-Ag NWs rapidly (10 min). Moreover, it is easy to realize large-scale preparation with this method. The NW composition can be adjusted readily to optimize their performance in the electrocatalytic methanol oxidization reaction (MOR). Compared with commercial Pt/C, NWs with appropriate Ag/Pt ratios exhibit high stability, activity, and CO tolerance ability.