The interaction between the radially polarized vectorial light and GO/AuNRs composite structures is studied to boost the SERS performance. Based on the simulation of the finite-difference time-domain solutions software, the SERS enhancement factor of the GO/single-AuNR composite substrate illuminated by the radially polarized light is up to 10 8, which is six orders of magnitude greater than that achieved by linearly polarized light under the same conditions. The physical mechanisms for this performance improvement are due to both the electromagnetic enhancement of gold nanorods excited by the radially polarized light and intrinsically chemical enhancement afforded by the GO film. Furthermore, the effects of different GO thicknesses and the number and arrangement of gold nanorods on the properties of SERS with radially polarization illumination are discussed in detail. The performance control of the SERS based on radial-vector light field bestirring the multifunctional substrate has great potential in biochemistry, food safety, and sensor detection.