In this report, electrospinning, impregnation and calcination processes were used to fabricate the Ni nanoparticles (NPs) loaded carbon nanofibers (CNFs) successfully. The nanofibers were characterized by infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The images indicated that the Ni NPs were well-dispersed on the surface of the CNFs. The catalytic behavior in the liquid phase hydrogenation of nitrotoluene to toluidine was studied. The superior activity of catalyst was attributed to the highly dispersed of Ni NPs with narrow particle size distribution.