Aqueous colloidal silver nanoparticles have substantial potential in biological application as markers and antibacterial agents and in surface-enhanced Raman spectroscopy applications. A simple method of fabrication and encapsulation into an inert shell is of great importance today to make their use ubiquitous. Here we show that colloids of silver-core/silica-shell nanoparticles can be easily fabricated by a laser-ablation-assisted chemical reduction method and their sizes can be tuned in the range of 2.5 to 6.3 nm by simply choosing a proper water-ethanol proportion. The produced silver nanoparticles possess a porous amorphous silica shell that increases the inertness and stability of colloids, which decreases their toxicity compared with those without silica. The presence of a thin 2 to 3 nm silica shell was proved by EDX mapping. The small sizes of nanoparticles achieved by this method were analyzed using optical techniques, and they show typical photoluminescence in the UV-vis range that shifts toward higher energies with decreasing size.