Numerous studies of the ionic conductivities in oxide-doped chalcogenaide glasses have shown the anomalous result that the ionic conductivity actually increases significantly (by more than a factor of 10 in some cases) by the initial addition of an oxide phase to a pure sulfide glass. After this initial sharp increase, the conductivity then monotonically decreases with further oxide addition. While this behavior is important to the application of these glasses for Li batteries, no definitive understanding of this behavior has been elucidated. To examine this effect further and more completely, the ionic conductivities of 0.5Li2S + 0.5[(1 − x)GeS2 + xGeO2] glasses have been measured on disc-type bulk glasses. The ionic conductivity of the 0.5Li2S + 0.5GeS2 (x = 0) glass was observed to increase from 4.3 × 10-5 (Ω cm)-1 to 1.5 × 10-4 (Ω cm)-1 while the activation energy decreased to 0.358 eV from 0.385 eV by the addition of 5 mol % of GeO2. Further addition of GeO2 monotonically decreased the conductivity and increased the activation energy. On the basis of our previous studies of the structure of this glass system, the Anderson and Stuart model was applied to explain the decrease in the activation energy and increase in the conductivity. It is suggested that the “doorway” radius between adjacent cation sites increases slightly (from 0.29(±0.05) Å to 0.40(±0.05) Å) with the addition of oxygen to the glass and is proposed to be the major cause in decreasing the activation energy and thereby increasing the conductivity. Further addition of oxides appears to contract the glass structure (and the doorway radius) leading to an increase in the conductivity activation energy and a decrease in the conductivity.