Ion exchange experiments and impedance spectroscopy investigations were performed on adducts of copper(I) halides to phosphorus and polyphosphorchalcogenide polymers, respectively. All compounds under investigation except one showed an ion exchange reaction (Cu+ <-> Ag+) in an aqueous silver nitrate solution at room temperature and are therefore considered to contain mobile copper ions. Impedance measurements on (CuI)(8)P-12, (CuI)(3)P-12 and Cu3P15I2 demonstrated that the total conductivity of (CuI)(8)P-12 and (CuI)(3)P-12 is predominantly ionic with corresponding activation energies of 0.45 and 0.59 eV,respectively, while the conductivity of Cu3P15I2 is mainly electronic with a related activation energy of about 0.72 eV.