ZnCl2[polyethylene oxide (PEO)](12), [0.33 ZnCl2 + 0.67 KCl](PEO)(12), and [0.33 ZnCl2 + 0.67 CsCl](PEO)(12) complexes were studied by x-ray absorption in the temperature range of 25 to 120 degrees C. The results for ZnCl2(PEO)(12) show that the complex exists mostly as undissociated ZnCl2 with the Zn atom also coordinated with four O atoms from the PEO. The respective Zn-Cl and Zn-O bond distances are 2.2 and 2.05 Angstrom. There is an increase in ion pairing with increasing temperature. The results for the mixed salt complexes are consistent with the formation of a mixture of ZnCl42- and ZnCl3- complexes with a Zn-Cl bond distance of similar to 2.26 Angstrom. Complex formation differs in [0.33 ZnCl2 + 0.67 KCl](PEO)(12) and [0.33 ZnCl2 + 0.67 CsCl](PEO)(12). This is attributed to the higher charge density of K+, which promotes ion pairing and shifts the ZnCl42-/ZnCl3- equilibrium.