The possibility of producing a biodegradable polymer electrolyte based on poly-ɛ-caprolactone (PCL) with different concentrations of LiClO4 has been investigated. The maximum ionic conductivity obtained at room temperature was 1.2×10−6 Scm−1 for PCL complexed with 10wt.% LiClO4. In this mixture, complete biodegradation occurred after 110 days and was attributed to the presence of ester groups in the polymer matrix. The large electrochemical stability window of approximately 5V showed that the PCL/LiClO4 electrolyte had important electrochemical properties that would make it useful in the production of rechargeable batteries with a lower environmental impact.