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New superionic glasses (CuI) x (AgPO 3 ) 12x with x ¼ 0.1, 0.2 and 0.3 have been prepared by rapid quenching method. Neutron diffraction experiments have been performed by a HIT-II spectrometer at the Neutron Spallation Source, KEK, Japan. A small first diffraction peak at low Q around 0.8 Å was observed in the structure factor for x ¼ 0.2 and x ¼ 0.3, but for x ¼ 0.1 it shows only a shoulder that is similar to the undoped glass AgPO 3 . Three new peaks appear at the radial distribution function of (CuI) x (AgPO 3 ) 12x at , 1.9, 2.7 and 3.4 Å , that may correspond to the CuZO, CuZI and CuZCu pair correlations, respectively. Those peaks increase with the amount of CuI. These results indicate that there are two different kinds of Cu atoms. CuZI bond in the glass is very similar to that in crystalline a-CuI, and CuZO bond is very similar to that in Cu 2 O insulating crystal.