Pt-based alloy nanoparticles/porous-structured nanofibers nanocomposites, Pt-Ni/pCNFs and Pt-Ag-Ni/pCNFs, were successfully prepared via electrospinning, dip-molding, carbonization and replacement reaction as electrocatalysts for methanol oxidation reaction (MOR). The alloy nanoparticles with average diameter of 180 nm were uniformly embedded on the surface of pCNFs. Taking advantages of the three factors alloy system and porous nanofiber structure, Pt-Ag-Ni/pCNFs catalyst exhibits the higher electrocatalytic activity for methanol (the maximum current density is ca. 19.6 mA cm(-2)) than that of Pt-Ni/pCNFs. In addition, Pt-Ag-Ni/pCNFs also shows an excellent electrocatalytic stability of methanol and superior sensitivity for methanol (0.0022 mA cm(-2) mM(-1)). A proposed mechanism of Pt-Ag-Ni/pCNFs for MOR was proposed in the research. This research could provide a novel strategy for the preparation of MOR electrocatalysts. (c) 2018 Elsevier B.V. All rights reserved.