Hybrid materials produced by the versatile sol-gel process with a wide sodium triflate, NaCF3SO3, concentration range have been studied. The host matrix of these xerogels, designated as di-ureasil and represented by U(600), is composed by a siliceous network bonded through covalent bonds to short polyether chains by means of bridging urea groups. The results obtained reveal that at high salt concentration, this system forms crystalline phases. The most conducting ormolyte exhibits a conductivity of 3.6 x 10(-7) Omega (-1) cm (-1) at room temperature. (C) 2003 Elsevier Science B.V. All rights reserved.