Several innovative platinum-based catalysts employing diverse metal–organic framework (MOF)-derived materials to alloy Pt with transition metals (Ni, Co) and integrating them into nitrogen-doped porous carbon (NPC) nanorod frameworks, NiCo@Pt/NPC, were prepared, which have unique properties for electrocatalytic methanol oxidation reaction (MOR). The structure properties of NiCo@Pt with NPC supporting layer were explored by several characterizations such as X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). Moreover, the structure–activity relationship of NiCo@Pt/NPC was carefully studied. The NiCo@Pt/NPC-T₈₀₀-X₁₅-t₁₅ exhibited exceptional performance of methanol oxidation, with a mass activity reaching 821.4 mA·mg_Pt⁻¹, 2.4 times higher than that of commercial Pt/C. Furthermore, compared with the commercial Pt/C, it maintained a steady current density 7.7 times higher. Compared with commercial Pt/C, the CO intermediate peak potential exhibited a 57-mV negative shift, primarily attributed to the interfacial effects between NiCo@Pt nanoparticles and NPC of the composite material, improving electron transport and preventing nanoparticle agglomeration, thereby considerably increasing MOR efficiency. This study provides innovative pathways for advancing Pt-alloy catalyst systems and novel approaches for the improvement of MOR catalysts.