Surface-enhanced Raman scattering (SERS) is a well-established surface-sensitive technique for detecting trace amounts of molecular analytes. While the impact of surface singularities on plasmonic materials has been widely studied, the fabrication of cost-effective, efficient SERS substrates remains a challenge. In this paper, we present the study of large-area nanorough Au SERS-active substrates, elaborated by thermal evaporation deposition by photoemission electron microscopy (PEEM), a high-resolution near-field mapping technique, to access the statistical properties of the hot-spot distribution. We experimentally demonstrate that the near-field PEEM and far-field Raman statistical signatures of nanorough Au surfaces are quantitatively correlated when used for molecular sensing. The maximum of the SERS signal of thiophenol (TP) molecules diluted to 10–6 M is observed near the film percolation threshold for which the hot-spot density is maximum. Finally, SERS measurements from solutions of TP, crystal violet, and rhodamine B molecules at 10–8 M demonstrated the sensitivity of our substrates for molecular sensing.