The electrochemical performance of Li-S cells was investigated in various ternary electrolyte solutions composed of 1,2-dimethoxyethane (DME), tetra(ethylene glycol) dimethyl ether (TGM), and 1,3-dioxolane (DOX). The discharge capacity values and cycle data obtained at each composition were statistically treated with the Minitab program to obtain mixture contour plots, from which the optimal composition of the ternary solvent systems was predicted. The discharge capacities and capacity retention were quite dependent on the electrolyte composition. It was estimated from the contour plots of the capacity at 1.0 C that the discharge capacity sharply increased with a decrease in the TGM content. High capacities greater than 900 mAh/g at 1.0 C were expected for the electrolyte composition with a volume ratio of DME/TGM/DOX = 1/0/1. In contrast, it was predicted from the mixture contour plot of the capacity retention that the cycle performance would significantly increase with an increase in the DME content.