Several lithium borates and lithium aluminates were prepared and were applied in Poly(ethylene oxide) (PEO)-based polymer electrolytes. The effects of the length of the oligoether chains, the kind of the electron withdrawing groups and the atoms of the ate-complex centers in the lithium salts on ionic conductivities of the polymer electrolytes were investigated, The results were explained by geometry calculation of lithium salts in MOPAC using PM5 parameter. High lithium ion transference numbers were determined for the lithium borate containing polymer electrolytes. They also exhibited satisfactory electrochemical stability for battery applications. (c) 2006 Elsevier B.V. All rights reserved.