A solid polymer electrolyte (SPE) based on polyethylene oxide (PEO) is prepared by photocuring of polyethylene glycol acrylates. The conductivity is greatly enhanced by adding low molecular weight poly(ethylene glycol) dimethylether (PEGDME). The maximum conducticity is 5.1×10−4 Scm−1 at 30°C. These electrolytes display oxidation stability up to 4.5V against a lithium reference electrode. Reversible electrochemical plating/stripping of lithium is observed on a stainless steel electrode. Li/SPE/LiMn2O4 as well as C(Li)/SPE/LiCoO2 cells have been fabricated and tested to demonstrate the applicability of the resulting polymer electrolytes in lithium–polymer batteries.