In this work, we report studies on the Si, N and O local bonding in silicon oxynitride films deposited by PECVD technique, with chemical compositions varying from SiO 2 to Si 3 N 4 , utilizing N 2 O+N 2 +SiH 4 and N 2 O+NH 3 +SiH 4 as precursor gaseous. The films are characterized by X-ray absorption near edge structure (XANES) at the Si-K, N-K and O-K edges, in order to determine the local structure and by Rutherford backscattering (RBS) spectroscopy to obtain their chemical composition. The results at the Si-K edge show, for the samples with lower nitrogen content, a homogeneous structure compatible with a random distribution of Si–N and Si–O bonds (random bonding model) and for the samples with higher nitrogen incorporation a structure composed by two phases compatible with the random mixture model (RMM). On the other hand, the analysis of the results at the N-K edge demonstrates two features, which are attributed to two different nitrogen sites, a trigonal Si 3 N 4 -like site and SiO 2 -like sites, corresponding to nitrogen substituting O in Si–O–Si bridges, which originate a resonant line (RL) in the XANES spectra at approximately 399.1eV. Finally, the results at the O-K edge show only one edge, attributed to O–Si bonds, independently of the N and O concentration, for both gaseous mixtures.