Surface plasmon resonance (SPR) is one of the main mechanisms of Surface Raman Enhance Scattering (SERS) and it will depend on the morphology and free carrier density of substrates, in many of discussions have been proved. Recently, the semiconductor copper(I) sulphide (Cu2S), the natural p-type semiconductor, exhibits remarkable SPR in the nearinfrared region and can be regards as best candidate for active SERS substrates. In this report, the successive ionic layer adsorption and reaction (SILAR) process will be used to synthesis Cu2S nanostructures from ZnO nanorods as template deposited by electrochemical reaction. To further manipulate the different carrier densities of Cu2S nanostructuress, the adjustment of Cu vacancy in Cu2S can be accomplished by thermal processes under noble gas. Taking 4-aminothiophenol (4-ATP) as probe molecule to measure the SERS performance by Cu2S nanostructures made in this fabrication and also examines the effect on SERS by adjusting Cu vacancy under an excited wavelength of 632.8 nm and light power of 15 mW. In fact, the modulation of Cu vacancy will positively correlate to the SPR frequencies and so could get the best enhancement factor under the limited condition of excited source. Therefore, our results could provide a new opportunity to use SERS to explore the molecule-semiconductor interaction, a fundamental but essential question for designing novel devices.