Basic investigations on the electrochemical behavior of alumosilicate zeolites were conduced in gas atmosphere and aqueous solution using impedance spectroscopy under in situ conditions where "zeolitically" bound water molecules are present in the channel and cage system. Natural stilbite (STI) and heulandite (HEU), zeolites of structure types with the same 4 - 4 = 1 building units, were used for these investigations. At a given temperature, well defined water partial pressures were applied in the gas atmosphere (in situ conditions) and the effect of polar organic molecules on conductivity was investigated. Furthermore, the effect of complete water saturation of the channel system on the Arrhenius type activation energy of conductivity was investigated in aqueous solution in comparison. The ion-exchange behavior of zeolite materials could be monitored under these conditions. These results show that, dependent on the different parameters affecting the zeolite conductivity behavior, they are applicable in the field of electrochemical analysis if these basic results on single crystals are transferable to polycrystalline materials.