The (PEO)(n)ZnCl2 system, in the range of concentrations n = 4-16 has been characterized by X-ray diffraction, TGA/DTA and electrochemical impedance spectroscopy (EIS). Considering these studies and some values reported in the literature a pseudo-equilibrium phase diagram has been drawn. An intermediate compound with a 4:1 composition appears to exist. The EIS conductivity measurements performed after rapid cooling of samples previously heated to above the transition temperature (T-t) indicated that retention of an amorphous phase below T-t is possible for short times.