A novel hierarchical nanostructure ofFe2O3-flaky coated carbon fibers was produced by the electrospinning process followed by a hydrothermal technique. First, electrospinning of a colloidal solution that consisted of ferric nitrate and polyacrylonitrile (PAN) was performed to produce PAN nanofibers. Then electrospun nanofiber was stabilized and calcinated in nitrogen at 800°C for 2 h to produce carbon nanofibers (CNFs) which were exploited to produceFe2O3-flaky structure using hydrothermal technique. The as-obtained products were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results revealed thatFe2O3flakes were successfully grown on the CNFs substrates, and the coverage ofFe2O3flakes could be controlled by simply adjusting the hydrothermal pH value and time.Fe2O3-flaky coated carbon fibers displayed high photocatalytic activity toward degradation of methyl orange (MO) under visible light irradiation.