Surface enhanced Raman scattering (SERS)-based nanoprobes have been used as well-established analytical tools enabling single-molecule detection. In this work, we report a facile method to decorate sea urchin-like gold nanoparticles (SUGNPs) on the surface of PMMA/P4VP nanofibers. Firstly, PMMA/P4VP nanofibers within the submicrometer size range were prepared by applying the electrospinning technique. Then, the incorporation of SUGNPs on the surface of PMMA/P4VP nanofiber was achieved by immersing PMMA/P4VP nanofiber into freshly prepared SUGNP aqueous solution through the specific Au-N interactions. The as-fabricated SUGNP-coated PMMA/P4VP nanofibers exhibited good sensitivity and reproducibility in SERS measurements with the relative standard deviation down to 6.6%, by employing 4-mercaptobenzoic acid as a probe molecule with 30 min of soaking time. Hence, we envisage that the SUGNP-coated PMMA/P4VP nanofibers can act as efficient and stable SERS substrates for potential applications in molecular detection as well as chemical and biological analysis. (c) 2021 Elsevier Inc. All rights reserved.