This paper describes the synthesis and characterization of three-dimensional hybrid inorganic–organic networks prepared by a polycondensation reaction between Zr(O(CH2)3CH3)4 and polyethylene glycol 400 (PEG400). Eleven hybrid networks doped with varying concentrations of LiClO4 salt were prepared. On the basis of analytical data and FT-Raman studies it was concluded that these polymer electrolytes consist of inorganic–organic networks with zirconium atoms bonded together by PEG400 bridges. These polymers are transparent with a solid rubber consistency and are very stable under inert atmosphere. Scanning electron microscopy revealed a smooth glassy surface. X-ray fluorescence microanalysis with energy dispersive spectroscopy demonstrated that all the constituent elements are homogeneously distributed in the materials. Thermogravimetric measurements revealed that these materials are thermally stable up to 262°C. Differential Scanning Calorimetry measurements indicated that the glass transition temperature T g of these inorganic–organic hybrids varies from −43 to −15°C with increasing LiClO4 concentration. FT-Raman investigations revealed the TGT (T=trans, G=gauche) conformation of polyether chains and allowed characterization of the types of ion-ion and ion–polymer host interactions in the bulk materials. The conductivity of the materials at different temperatures was determined by impedance spectroscopy over the 20 Hz–1 MHz frequency range. Results indicated that the materials conduct ionically and that their ionic conductivity is strongly influenced by the segmental motion of the polymer network and the type of ionic species distributed in the bulk material. Finally, it is to be highlighted that the hybrid network with a n Li/n O molar ratio of 0.0223 shows a conductivity of ca. 1×10−5 S cm−1 at 40°C.