Structural characterization studies using Raman and i.r. spectroscopy and extended X-ray absorption fine structure (EXAFS) on the (PEO)(n)[(ZnBr2)(1-x)(LiBr)(x)] system (n = 20, 40; x = 0-0.8) are reported. Raman spectroscopy reveals that the ionic species present in the complex depend on the Zn:Li ratio and the ether oxygen to metal ion ratio. With increasing x values, the species vary from ZnBr2 to ZnBr3- to ZnBr42-. EXAFS measurements confirm that the Zn-Br coordination number is higher for the (PEO)(n)[(ZnBr2)(1-x)(LiBr)(x)] system than the (PEO)(n)ZnBr2 system. In the (PEO)(20)[(ZnBr2)(0.2)(LiBr)(0.8)] composition, no oxygen neighbours of zinc are apparent while a significant Zn-O contribution is present in the (PEO)(40)[(ZnBr2)(0.6)(LiBr)(0.4)] and (PEO)(40)ZnBr2 complexes. Temperature dependent EXAFS measurements of (PEO)(20)[(ZnBr2)(0.2)(LiBr)(0.8)] show that ionic association is not altered with lowering of temperature. The effect of addition of tetraethylene glycol (TEG) and its dimethyl ether (TEGDME) to the complex is also reported.