In this paper, a new type glassy solid electrolyte is reported, which is based on silver iodide with monomer organic ions. Glass preparations were tried by rapidly quenching the melts of the silver iodide (AgI), tetraethylammonium iodide (TEAI), tetramethyl-ammonium iodide (TMAI) and CsI systems. The glass formations were confirmed by X-ray diffraction, DSC and polarized microscope. Glass forming regions were discovered in the system of AgI-TMAI-TEAI and AgI-TMAI-CsI. The ionic conductivity values of those glasses are in order of 10-2 ohms-1 cm-1 a room temperature. These new glasses exhibit high ionic conductivity comparable to the oxide based superionic glasses, and 10 to 10000 times larger than those of typical Li+ conducting polymer electrolytes.