In this paper, the electrospun Ag nanoparticles and g-C-3N4 (Ag/g-C3N4) loaded composite carbon nanofibers were successfully prepared combing the electrospinning technology and carbonization treatment. The composition and microstructure of the resultant composite nanofibers were characterized by x-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive spectrometer (EDS), transmission electron microscopy (TEM) and x-ray photoelectron spectrometry (XPS). Due to the synergistic effect between catalytic activity of Ag nanoparticles (NPs) and g-C3N4 and excellent adsorption capacity of carbon nanofibers, the resultant electrospun Ag/g-C3N4 loaded composite carbon nanofibers exhibited excellent conversion of 4-nitrophenol to 4-aminophenol and benzylamine to N-benzylbenzaldimine. The resultant hybrid carbon composite nanofibers offer the significant advantages, such as low dosage, high catalytic activity, easy recycling and excellent stability.