Structural analysis of xAg(2)O center dot (100 - x) [2B(2)O(3) center dot As2O3] glass system, with 0 <= x <= 10 mol%, was performed by means of FT-IR and Raman spectroscopies. The purpose of this work is to investigate the structural changes that appear in the 2B(2)O(3) center dot As2O3 glass matrix with the addition and increase of silver ions content. Boroxol rings, pyro-, ortho-, di-, tri-, tetra-, and pentaborate groups, structural units characteristic to As2O3 were found in the structure of the studied glasses. FT-IR spectroscopy measurements show that BO3 units are the main structural units of the glass system. The presence of structural units characteristic to Ag2O were not directly evidenced by FT-IR spectroscopy. Raman analysis leads to similar conclusions as that obtained from FT-IR measurements.