Lithium conductivity in PEO-LiClO4 salt-phenolic electrolytes was measured by a four-probe method using the complex impedance method at ambient temperature. Measurements were made for 5.0. 10.0, and 15.0 wt% LiClO4 series. The electrolytes exhibited outstanding conductivity currents at ambient temperatures. This effect was attributed to the reduced PEO crystallinity and lower pseudo activation energy in lithium transfer.