The glass samples of the Ge-S-I system were synthesized by plasma-enhanced chemical vapor deposition (PECVD) in a low-temperature non-equilibrium RF-plasma discharge. The vapors of S and GeI4 were the initial substances. The process was carried out in a flowing quartz reactor at the walls temperature of 300-500 °C and the total pressure range of 1.9-22.8 Torr. The phase and the elemental compositions of the deposited glassy batches were investigated. The glasses obtained by melting of the solid reaction products were homogenized in the evacuated quartz glass ampoule and they were studied by DSC, X-ray microanalysis, and atomic emission spectroscopy. The proposed method allows to prepare the glasses of the system Ge-S-I with Si content less than 3 ⋅ 10−5 wt.%.