Raman spectra of GeS2 -Ga2S3-KCl pseudo-ternary system glasses at room temperature in the air were probed systematically in the region of 150-500 cm(-1). Based on the results of Raman spectra and preparing procedure in pseudo-binary systems GeS2 -KCl and Ga2S3 -KCl, the sole interaction of Ga2S3 and KCl was identified and new units GaS3/2 Cl were produced in GeS2 -Ga2S3-KCl glasses. That K+ ions in the form of Cl as the nearest coordination were homogeneously dispersed in the polymeric network was confirmed by the Raman spectra evolution of samples on the serials I and Ill. Raman spectral evolution of three composition serials can be successfully interpreted using a localized model considering the effect of K+ ions on the structural units GaS3/2 Cl and Ga2 S4 Cl2.