This study presents a “modified polyol” approach for the synthesis of silver nanoparticles (AgNPs) utilizing a synergistic citrate-glycerol system. Glycerol functions as a non-toxic solvent, mild co-reductant, and stabilizing medium, while citrate serves as a secondary stabilizer to ensure colloidal stability through electrostatic repulsion. The formation of AgNPs were systematically monitored via UV-Vis spectroscopy to determine optimal synthetic parameters. The crystalline structure, surface chemistry, and morphological attributes of the synthesized nanoparticles were systematically characterized using X-ray diffraction (XRD), selected area electron diffraction (SAED), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM), confirming the production of phase-pure silver crystals with a spherical morphology and a well-defined average diameter of 9.5 nm. The catalytic evaluation of AgNPs was evaluated through the aqueous reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) utilizing NaBH4. Using a low catalyst loading of 0.10 ppm, a 92% degradation efficiency was achieved within 6 minutes. Kinetic analysis followed a pseudo-first-order model, yielding an apparent rate constant of 0.4673 +/- 0.0095 min-1 (n = 3). These results underscore their high catalytic activity, positioning this sustainable synthesis for pollutant removal and the transformation of toxic industrial waste into valuable chemical precursors.