We report results from our extensive studies on the fabrication of ultra-thin, flexible, and cost-effective Ag nanoparticle (NP) coated free-standing porous silicon (FS-pSi) for superior molecular sensing. The FS-pSi has been prepared by adopting a simple wet-etching method. The deposition time of AgNO3 has been increased to improve the number of hot-spot regions, thereby the sensing abilities are improved efficiently. FESEM images illustrated the morphology of uniformly distributed AgNPs on the pSi surface. Initially, a dye molecule [methylene blue (MB)] was used as a probe to evaluate the sensing capabilities of the substrate using the surface-enhanced Raman scattering (SERS) technique. The detection was later extended towards the sensing of two important explosive molecules [ammonium nitrate (AN), picric acid (PA)], and a pesticide molecule (thiram) clearly demonstrating the versatility of the investigated substrates. The sensitivity was confirmed by estimating the analytical enhancement factor (AEF), which was ∼107 for MB and ∼104 for explosives and pesticides. We have also evaluated the limit of detection (LOD) values in each case, which were found to be 50 nM, 1 µM, 2 µM, and 1 µM, respectively, for MB, PA, AN, and thiram. Undeniably, our detailed SERS results established excellent reproducibility with a low RSD (relative standard deviation). Furthermore, we also demonstrate the reasonable stability of AgNPs decorated pSi by inspecting and studying their SERS performance over a period of 90 days. The overall cost of these substrates is attractive for practical applications on account of the above-mentioned superior qualities.