Two types of Pt nanoparticle electrocatalysts were composited on Pt nanowires by a combination of an electrospinning method and an impregnation method with NaBH4 as a reducing agent. The structural properties and electrocatalytic activities for methanol electro-oxidation in direct methanol fuel cells were investigated by means of scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. In particular, SEM, HRTEM, XRD, and XPS results indicate that the metallic Pt nanoparticles with polycrystalline property are uniformly decorated on the electro-spun Pt nanowires. In order to investigate the catalytic activity of the Pt nanoparticles decorated on the electro-spun Pt nanowires, two types of 20 wt% Pt nanoparticles and 40 wt% Pt nanoparticles decorated on the electro-spun Pt nanowires were fabricated. In addition, for comparison, single Pt nanowires were fabricated via an electrospinning method without an impregnation method. As a result, the cyclic voltammetry and chronoamperometry results demonstrate that the electrode containing 40 wt% Pt nanoparticles exhibits the best catalytic activity for methanol electro-oxidation and the highest electrochemical stability among the single Pt nanowires, the 20 wt% Pt nanoparticles decorated with Pt nanowires, and the 40 wt% Pt nanoparticles decorated with Pt nanowires studied for use in direct methanol fuel cells.