A silver (Ag) target was ablated using the XeCl excimer laser at room temperature in vacuum. Films were deposited on the Si(111) substrates parallel to the target surface. The scanning electron microscopy, X-ray diffraction (XRD), and selected area electron diffraction analysis results denote that the deposited films comprise Ag nanoparticles with different sizes. The fixed laser fluence increases the distance from the target to the substrate, decreases the nanoparticle size and depth of the film, and weakens the combinative extent of the nanoparticles. Further, the XRD spectrum intensity of the crystallographic face of (111) decreases, whereas that of the crystallographic face of (200) increases. When the distance from the target to the substrate is fixed, the nanoparticle size and depth of the film increases with the increasing laser fluence, and the combinative extent of the nanoparticles increases. The XRD spectrum intensity of the crystallographic face of (111) increases, whereas that of the crystallographic face of (200) barely decreases. Furthermore, the experimental results are analyzed on the basis of the nucleation and transition of the nanoparticles, mobility of the ablated particles, and surface energy required in film growth along different crystallographic faces.