The hybrid polymer thin film has been prepared by composing of poly(vinyl chloride), lithium salts and plasticizer and used as a solid polymer electrolyte(SPE). The phase transition temperature(Tg) was determined by differential scanning calorimetry (DSC). The ionic conductivities of the electrolyte at various temperatures have been investigated by a.c. impedance spectroscopy, and shown as 10(-4)similar to 10(-3) ohm(-1). cm at room temperature. And a new secondary lithium cell, Li/FeOOH(an) employed with the prepared solid polymer electrolyte has shown the open-circuit voltage of 3.10 V, capacity of 69 mAh/g, and energy density of 179 Wh/kg, respectively. In addition, the kinetic and impedance parameters and electrochemical characteristics of Li/SPE/FeOOH(an) cell at the discharge/charge process have been studied.