Silver nanoparticles of high chemical homogeneity have been synthesized by a novel laser–liquid–solid interaction technique from a solution composed of silver nitrate, distilled water, ethylene glycol, and diethylene glycol. Rotating nickel, niobium, stainless steel, and ceramic Al2O3 substrates were irradiated using a continuous-wave CO2 laser and Q-switched Nd–YAG laser (λ = 1064 and 532 nm). The silver nanoparticles were characterized using x-ray diffraction (XRD), scanning electron microscopy (SEM), and electron probe x-ray microanalysis (EPMA). The shape of silver particles was dependent on the chemical composition and laser parameters. The synthesis mechanism of silver nanoparticles has been proposed to occur primarily at the laser–liquid–substrate interface by a nucleation and growth mechanism.