A high-energy X-ray diffraction study has been carried out on a series of 0.5Li2S + 0.5[(1 − x)GeS2 + xGeO2] glasses with x = 0.0, 0.1, 0.2, 0.4, 0.6 and 0.8. Structure factors were measured to wave vectors as high as 30 Å−1 resulting in atomic pair distribution functions with high real space resolution. The three dimensional atomic-scale structure of the glasses was modeled by reverse Monte Carlo simulations based on the diffraction data. Results from the simulations show that at the atomic-scale 0.5Li2S + 0.5[(1 − x)GeS2 + xGeO2] glasses may be viewed as an assembly of independent chains of (Li+ -S)2GeS2/2 and (Li+ -O)2GeO2/2 tetrahedra as repeat units, where the Li ions occupy the open space between the chains. The new structure data may help understand the reasons for the sharp maximum in the Li+ ion conductivity at x ∼ 0.2.