A carbon nanofibers (CNFs)-supported palladium nanoparticles (Pd NPs) catalyst was fabricated by the combination of electrospinning, gas-phase hydrogenation reduction and subsequent calcination processes. Extensive characterization of the resulting carbon nanofibers-supported palladium nanoparticles catalyst was carried out. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) images reveal that the spherical Pd NPs are well-dispersed on the surfaces of the carbon matrix or embedded in the carbon matrix without agglomerating. The cubic phase of Pd formed during the reduction and carbonization processes. Most importantly, this carbon nanofibers-supported palladium nanoparticles hybrid material exhibited enhanced activity, excellent stabilization and recyclability.