High-power excimer-laser irradiation (248 nm wavelength) at different energy densities (1.3, 2.3, and 4.6 J/cm2) has been performed on silver-exchanged soda-lime glass. Silver nanoclusters have been obtained with average size depending on the energy density of the laser pulses. The excimer laser pulses induce either the reduction of the silver ions or the heating of the irradiated glass matrix. The high mobility of silver atoms in the liquid phase and the segregation effects at the liquid–solid interface can explain the observed silver atoms clustering.