Chalcogenide thin films (GeSe2)100 − x(Sb2Se3)x (with x = 10 and 50) were deposited by Radio-frequency (RF) magnetron sputtering. In order to study the impact of Ar pressure on the structure and the composition of selenide thin films structural properties of thin films and targets were investigated by means of Raman scattering spectroscopy and X-ray photoelectron spectroscopy (XPS). Under low pressure (5 · 10− 3 mbar), the increase of wrong bonds like Ge(Sb)-Ge(Sb) was confirmed by Raman and also XPS for both composition. The observed structural changes with Ar pressure are linked with modification of the composition of the selenide films analyzed by EDS and XPS. Furthermore for higher Ar pressure (5 · 10− 2 mbar), RF sputtered thin film and target structure present a great similarity. These differences driven by Ar pressure modification are probably related to distinctive sputtering rate and mean free path of the particles ejected from target for the different Ar pressures.