X-ray absorption (XAS) studies of ZnBr2-PEO complexes, at the Zn K edge, at temperatures between 25 and 120 degrees C, indicate that additions of bromide salts of Li, Rb, or Ca result in the formation of ZnBr4= complexes with a Zn-Br bond length of 2.42 Angstrom. XAS, at the Rb K edge, in mixed RbBr/ZnBr2-PEO complexes with an excess of ZnBr2, shows that the ZnBr2 causes the RbBr to dissolve in the polymer The Rb+ ions are weakly complexed with the PEO with an Rb-O bond distance of 2.93 Angstrom.