The synthesis of Li2PdCl4 and Li3Fe(CN)6 precursors, and the preparation of the first lithium Z-IOPE material obtained by reacting these precursors with poly(ethylene glycol)600 (PEG600) is reported. This new material has been obtained through a sol⇒gel and gel⇒plastic transition. FIR and MIR spectroscopy studies, Raman laser and UV–vis investigations and detailed compositional data allowed us to propose a structural hypothesis and to detect the interactions between ions and the coordinating segments of the host network. It has been concluded that: (1) this compound is a mixed inorganic–organic network in which clusters formed by palladium and iron complexes are bonded together by PEG bridges; (2) the conformation of polyether chains in the bulk material is of the TGT (T=trans, G=gauche) type. The conductivity of the proposed [FexPdy(CN)zClv(C2nH4n+2On+1)Lil] is ≈5.3×10−5 S cm−1 at 35.1°C.