Large area ordered Fe2O3@Ag nanorod arrays were prepared via hydrothermal method and ion sputtering method based on the uniformly ordered polyacrylonitrile (PAN) nanopillar array films. The morphology and structure of the substrate were characterized by scanning electron microscope, transmission electron microscope, energy dispersive spectrometer, UV-Vis absorption spectrometer and X-ray diffractometer. The SERS activity of the Fe2O3@Ag nanorod arrays was studied by Raman spectrometer with rhodamine 6G (R6G) and 4-Aminothiophenol (4-ATP) as probe molecules. As a result, 10-10 M R6G and 10-9 M 4-ATP can be SERS recognized respectively. In addition, with 10-6 M 4-ATP as the probe molecule, the relative standard deviation (RSD) of SERS signal is 7.5%, which shows that the prepared substrate has high SERS activity and signal uniformity. Therefore, the prepared ordered Fe2O3@Ag nanorod arrays have great potential in SERS detection.