Nanostructured silver thin films were prepared by radio frequency magnetron sputtering at room and liquid nitrogen substrate temperatures. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) were employed to study the topography and chemical composition, respectively, of the thin films. The AFM results indicate a significant difference in the morphology of the thin films when argon or nitrogen ions were used as sputtering ions. For argon ion sputtering, a difference also exists in the microstructure and topography of the thin films for ambient and liquid nitrogen substrate temperatures. The XPS results show a high purity of nanostructured silver thin films for sputtering by both argon ions and nitrogen ions, but with some oxygen and carbon contamination. For argon ion sputtering, the content of oxygen and carbon is less than 6.9% and 4.5%, and for nitrogen ion sputtering, less than 4.7% and 3.6%.