Glassy fast ionic conductors can be used as solid electrolytes, cathode materials, conducting fibers and electrochromic glasses due to their high ionic conductivity and good transparency. While the conductivity of the conductors is highly dependent on the organization of glass networks, it is very difficult to finely characterize the glass structure, and thus the relation between the conductivity and glass structures has rarely been reported. Solid-state nuclear magnetic resonance (NMR) is extremely suitable for probing glass structures due to its flexible and comprehensive capabilities in detecting the structure information of vitreous materials at the atomic scale.