Thin films were prepared using glass precursors obtained in the ternary system NaPO3-BaF2-WO3 and the binary system NaPO3-WO3 with high concentrations of WO3 (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L-I and L-III absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO6) and that these films are free of tungstate tetrahedral units (WO4). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO6 octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (above 40% molar) attributed to the formation of WO6 clusters. (C) 2008 Elsevier B.V. All rights reserved.