The rapidly growing global energy demand, especially for energy from renewable sources, requires development of longer-lasting, safer, and smaller batteries. Ion-conducting glasses are of particular interest as candidates for solid electrolyte materials in next-generation batteries. Commercial solid-state electrolytes require an ionic conductivity of at least 10-3 S/cm. In order to meet this design constraint, development of new ion-conducting glasses is required. An increase or decrease in the ionic conductivity of glasses can be achieved by mixing two glass former cations at constant fraction of the mobile cation, known as the mixed glass former effect (MGFE). This enhancement or depression of the ionic conductivity is non-linear and non-additive, and its cause is currently unknown. The 0.5Na2S + 0.5[xGeS2 + (1-x)PS5/2] glasses exhibit a negative MGFE in Na+ ion conductivity. If the cause of this depression in the Na+ ion conductivity is better understood, it may enable the design of mixed glass former systems that will exhibit enhancement of the ionic conductivity. We hypothesis that changes in short range order structures occur when the thio-phosphate and thio-germanate glass networks are mixed, causing the negative MGFE. Our comprehensive study of the glass structure and physical properties of the 0.5Na2S + 0.5[xGeS2 + (1-x)PS5/2] glasses shows that structural changes in the ternary glasses strongly correlate with the decrease in the ionic conductivity.