The conductivities of polymers like poly (vinyl alcohol) (PVA) and its iodine complex membranes are reported here. PVA-iodine complex membrane was prepared by dipping PVA film into an I-2-KI solution. The formation of the complex membrane was confirmed by IR spectra. Conductivities were determined from 30 to 300 degrees C with a frequency ranges from 42 Hz to 500 KHz in solid state. It was observed that iodine is known to act as a catalyst for dehydration of PVA. A possible mechanism for the dehydration of PVA catalyzed by iodine is also explained.