A novel of GaxGe(4-x)Sb64S128-40AgI glass system was prepared by melting quenching in the synthesis range of 0 ≤ x ≤ 4. The structure property, thermal behavior and electrical conductivity of the prepared glasses were investigated with the different Ge/Ga ratios. From the XRD pattern, there is no crystal precipitated from the sample material, and a slightly gallium element doping induced [GaS4] tetrahedral structure units and edge-shared [Ge(Ga)S(4−x)Ix] mixed structure facilitated the transport of ion channels. The glass conductivity overall increased with the addition of gallium content, glass with x=1 presented the highest conductivity of 9.18 × 10−6 S/cm at room temperature. These phenomenon and results offer a new thought to explore metal-doped sulfur solid electrolytes in batteries.