Carbon nanofibers supported copper nanoparticles (CuNPs/CNFs) catalyst was synthesized by electrospinning in the high-pressure hydrogenation method, and the high-temperature calcination. The catalyst was characterized by scanning electron microscope, transmission electron microscope, energy dispersive spectrometer, and X-ray photoelectron spectroscopy. The CuNPs/CNFs catalyst was used for Ullmann-type couplings under ligand-free conditions, and the results showed that the CuNPs/CNFs catalyst had a good catalytic activity for Ullmann O-arylation of aryl halides with various phenols. The schematic illustration: Preparation process of CuNPs/CNFs catalyst. [GRAPHICS] .