Nanostructured, Si-based cottonlike, highly porous thin films of Si, SiNx, and SiOx were deposited by the excimer laser ablation of Si targets in He, He∕N2, and He∕O2 ambients, respectively. Photoluminescence (PL), x-ray photoelectron spectroscopy, and photoacoustic Fourier transform IR have been used to characterize these deposits. After exposure to air, broad PL bands appear at 1.7eV (Si), 2.0eV (SiNx), and 2.3eV (SiOx); air oxidation causes the separation of the PL spectra into two identical component peaks, at 1.5 and 2.3eV, whose relative ratios differ with film composition. The present results indicate that the red PL peak at 1.5eV is due to the localized states at the oxidized surfaces of these materials, while the green PL peak at 2.3eV is due to oxygen-related defects in their local disordered nanostructures.