The photoluminescence (PL), time-resolved photoluminescence (TRPL) and PL-excitation (PLE) spectra of superionic conductor glass (AgI) 0.85 (Ag 2 WO 4 ) 0.15 have been measured at different temperatures between 8 K and room temperature. The PL intensity peak is observed at 426 nm which corresponds to free exciton wavelength of pristine AgI. There are also different PL bands well related to the internal and interface states of mesoscopic AgI particles in Ag 2 WO 4 glass matrix. This may give important information about the origins of superionic conduction. With increasing excitation light intensity, the PL efficiencies of several emission bands become saturated, except for the free exciton band.