The glass forming region of the system was explored as a function of lithium ion concentration. The most conductive base glass attainable was , and with this glass, up to could be added. Ionic conductivity was measured using complex plane techniques with room temperature conductivity reaching for . NMR linewidth data were fit to the Hendrickson‐Bray equation, and activation energies were obtained. All glasses showed a low activation energy process which was attributed to a local motion. Only the more conductive 30–40% glasses showed a second, higher activation energy process which correlated well with activation energies from conductivity measurements.