Microstructures of the noncrystalline copper ionic conductors with the network former of P2O5 were studied by means of transverse EXAFS, IR and Raman spectra. From the results, it is derived that in these noncrystalline network structure, there are skeleton structure elements such as PO43-, CuO4-6, CuO3I5-, PO312- etc., and there are two different distributions for Cu+ ions in voids of the network. The second-order phase transition of the materials at about 50℃ and conduction properties of Cu+ ions are discussed.