Star-shaped oligo(ethylene glycol) methyl ethers (three and four arm molecules of various molecular weights) were synthesized and characterized with regard to viscosity, thermal transitions, ability to solvate the electrolyte LiCF3SO3 and the ionic conductivity of their LiCF3SO3 solutions in comparison to linear oligo(ethylene glycol) methyl ethers. Polymer gel electrolytes were prepared by photopolymerization of tri(ethylene glycol) dimethacrylate (EG(3)DMA) or its copolymerization with the polar comonomer cyanomethyl methacrylate (CyMA) in the presence of the oligo(ethylene glycol) ethers mentioned above and of the electrolyte LiCF3SO3. The gels were characterized concerning their thermal transitions, thermo-mechanical properties, their ability to solvate the electrolyte and their ionic conductivity. In comparison to the linear plasticizers the star-shaped ones show a distinctly lower tendency to crystallize, which is even completely suppressed in several cases. Intensified ion association was found in LiCF3SO3 solutions of the star-shaped plasticizers, if the number of the ethylene glycol units per arm was lower than 4. Therefore, the conductivity of the solutions and the gels was lower than that with linear plasticizers at room temperature. The modification of the polymer matrix by copolymerization with 20 mol% CyMA resulted in a maximum of the ionic conductivity sigma approximate to 1 x 10(-5) S/cm of gels with star-shaped plasticizers at 25 degreesC. (C) 2004 Elsevier B.V. All rights reserved.