The poly(ethylene oxide) polymer (PEO) is doped with fine powder of MnCl2 salt and thin films of thickness (50–150 mm) with salt content (0, 5, 10, 15, and 20 wt%) are obtained. The AC electrical conductivity and dielectric constants are studied as a function of temperature through an impedance technique. It is found that AC conductivity increases and the calculated activation energy decreases with increasing temperature due to enhancement of the ionic conduction in the film bulk. The dielectric constants of the doped membranes increase with temperature. It is found that the peak value of the tanloss is shifted to a higher frequency at higher temperatures. The dielectric behavior is explained on the basis of interfacial (space charge) polarization, dipolar polarization, and hindrance of the polymer matrix.