The composite nanofibers from Au nanoparticles/carbon nanofibers (Au/CNFs) were fabricated through electrospinning, chemical reduction and high-temperature calcination methods. The polyacrylonitrile acted as the carbon precursor polymer. A series of characterization methods, which include UV-Vis diffuses reflectance spectra, UV-Vis spectra, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray diffraction respectively, were used to investigate the morphology and properties of catalysts. The result showed that the gold nanoparticles were well-distributed in/on the CNFs. In the end, the composite material was applied to epoxidation of styrene to investigate its catalytic activity.