This work describes a novel, one-shot strategy to fabricate ultrasensitive SERS sensors based on silver/poly(methyl methacrylate) (PMMA) nanocomposites. Upon spin coating of a dispersion of PMMA and silver precursor on N-doped silicon substrate, closely separated silver nanoparticles were self-assembled into uniform nanospheres. As a result, a thin hydrophobic PMMA layer embedded with Ag nanoparticles (AgNPs) was obtained on the whole silicon substrate. Consequently, a large-scale, reproducible SERS platform was produced through a rapid, simple, low-cost, and high-throughput technology. In addition, reproducible SERS features and high SERS enhancement factors were determined (SEF ~1015). This finding matches the highest SEF reported in literature to date (1014) for silver aggregates. The potential and novelty of this synthesis is that no reducing agent or copolymer was used, nor was any preliminary functionalization of the surface carried out. In addition, the AgNPs were fabricated directly on the substrate’s surface; consequently, there was no need for polymer etching. Then, the synthetic method was successfully applied to prepare opaque SERS platforms. Opaque surfaces are needed in photonic devices because of the absence of secondary back reflection, which makes optical analysis and applications easier.