Solid polymer electrolytes (SPEs) synthesized by the sol–gel process and designated as di-ureasils have been prepared through the incorporation of lithium perchlorate, LiClO4, into the d-U(2000) organic–inorganic hybrid network. Electrolytes with lithium salt compositions of n (where n indicates the number of oxyethylene units per Li+ ion) between ∞ and 0.5 were characterized by conductivity measurements, cyclic voltammetry at a gold microelectrode, thermal analysis and Fourier transform Raman (FT-Raman) spectroscopy. The conductivity results obtained suggest that this system offers a quite significant improvement over previously characterized analogues doped with lithium triflate [S.C. Nunes, V. de Zea Bermudez, D. Ostrovskii, M.M. Silva, S. Barros, M.J. Smith, R.A. Sá Ferreira, L.D. Carlos, J. Rocha, E. Morales, J. Electrochem. Soc. 152 (2) (2005), A429]. “Free” perchlorate ions, detected in all the samples examined, are identified as the main charge carriers in the sample that yields the highest room temperature conductivity (n =20). In the di-ureasils with n ≤10 ionic association is favoured and the ionic conductivity drops.