The effects of pulsed laser annealing on the structural and electron field emission (FE) properties of Ag–SiO2 nanocomposites are reported. The nanocomposites were synthesized by Ag+ implantation into thermally oxidized Si substrates with a dose of 7×1016 Ag+/cm2. The annealing was performed using a 248 nm KrF excimer laser. Multiple pulses, with duration of 25 ns, at an energy density of 250 mJ/cm2 were accumulated onto the same area of the sample. Surface protrusion structures of the as-implanted samples, causing geometrical field enhancement, are eliminated after laser annealing, and a reduction in concentration and coalescence of the Ag nanoclusters is observed from atomic force microscopy and transmission electron microscopy measurements. The threshold field for emission for the as-implanted sample is altered from 28 to 104, 16, and 35 V/μm after annealing with 5, 10, and 20 laser pulses, respectively. The FE properties of laser annealed samples are discussed in terms of two distinct field enhancement effects using their structural properties.