Zinc triflate (Zn(CF3SO3)(2))-doped sol-gel derived di-urea cross-linked POE/siloxane ormolytes (designated as di-ureasils) with infinity > n >= 1 (where the salt content is expressed as n, the molar ratio of oxyethylene moieties to Zn2+ ions) were investigated. The hybrids with n > 5 are entirely amorphous; those with n > 10 are thermally stable up to approximately 305 C. The siliceous network of representative samples (n = 200 and 10) is essentially composed of (SiO)(3)Si(CH2)-environments and is thus highly branched. The distance between the structural units in samples with 200 >= n >= 10 and n <= 7 is 4.2 and 4.3 angstrom, respectively. The estimated interdomain distance is 11 and 13 angstrom for xerogels with 200 >= n >= 20 and n <= 10, respectively. At n = 1 a crystalline POE/Zn(CF3SO3)(2) complex of unknown stoichiometry is formed. The conductivity maxima are located at n = 60 (3 x 10(-6) S cm(-1)) and n = 20 (7 x 10(-5) S cm(-1)) at 30 and 100 degrees C, respectively. (c) 2006 Elsevier Masson SAS. All rights reserved.