The expansive potential of surface-enhanced Raman scattering (SERS) has been well-established; however, the primary bottleneck hindering its routine analytical and commercial implementation is the poor signal reproducibility and challenges in substrate fabrication. Thus, the current work attempts to synthesize a scalable and reproducible nanoporous gold (npAu) decorated with gold (Au) nanoparticles to generate a highly structured Au@npAu nanocomposite. The substrate fabrication completes via three distinct routes: i) selective dealloying to form npAu on the Au film, ii) the fast deposition (i-t = −0.8 V, t = 10.0 s) of Au atoms across the npAu surface, and finally iii) the precise growth control of the generated Au@npAu by a series of by oxidation-reduction cycles (−0.03 to −0.4 V for 80.0 segments at ν = 50.0 mVs−1). The simulations of the dealloyed npAu and the final Au@npAu nanocomposite showed that the reduced interparticle spacing and ligament size in the Au@npAu nanocomposite is crucial for forming abundant "hot spot" regions with highly concentrated electromagnetic fields. The Au@npAu substrate reproducibility was assessed on 400.0 sites for SERS spectral acquisition with a relative standard deviation of 9.22 %. Furthermore, the Au@npAu was checked under different preparation batches for intra- and inter-day analysis and storage for 20.0 days with good stability. Finally, the substrate was checked for direct SERS detection of ferbam residues with a 4.34 × 10−9 mol L−1 sensitivity and examined in real samples with satisfactory recoveries (97.63 ± 1.95%–99.16 ± 0.24 %). This work offers a promising avenue towards highly reproducible, scalable and universal Au@npAu SERS substrate fabrication in diverse SERS-related applications.
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