In this paper, the ordered mesoporous carbon nanofiber arrays (MCNAs), Nickel-Boron (Ni-B) amorphous alloys, and amorphous Ni-B/MCNAs composite for supercapacitor material have been successfully fabricated by a combination of templating method and chemical reduction process. The porous structure and large specific surface area (1270 m(2) g(-1)) of MCNAs favor the utilization of the active material Ni-B amorphous alloys and interfacial charge transport, and provide short diffusion paths for ions. X-ray diffraction, small-angle X-ray scattering, inductively coupled plasma. Transmission electron micrographs and selected area electronic diffraction were taken to characterize the structure of the ordered MCNAs, Ni-B amorphous alloy, and amorphous Ni-B/MCNAs. Electrochemical properties are characterized by cyclic voltammetry, galvanostatic charge/discharge measurements, and electrochemical impedance spectroscopy. The results show that the amorphous Ni-B/MCNAs display superior capacitive performance (733 F g(-1)) over Ni-B amorphous alloys (562 F g(-1)) at a scan rate of 5 mV s(-1) and a good cycling stability after 1000 cycles.