In this study the sol-gel synthetic strategy was used to prepare organic-inorganic hybrid electrolyte systems composed of a di-urea cross-linked poly(ethylene oxide) (PEO)/siloxane (di-ureasil) matrix with a wide concentration range of lithium tetrafluoroborate (LiBF(4)). The assembly and preliminary characterization of a prototype solid-state electrochromic device based on a four-layer sandwich structure incorporating these hybrid electrolytes doped with controlled quantities of LiBF(4) are reported. The composition of hybrid xerogels was indicated using the notation d-U(900)(n)LiBF(4) and d-U(600)(n)LiBF(4). In this representation the average molecular weight of the host di-ureasil framework is identified as d-U(900) or d-U(600) and the subscript n expresses the salt content in terms of the number of ether oxygen atoms per Li(+) cation. The most conducting electrolyte of these hybrid systems is the d-U(900)(35)LiBF(4) composition (1.70 x 10(-4) S cm(-1) at about 95 degrees C). The lowest decomposition temperature was observed at a composition of n 2.5 in both the d-U(900)(n)LiBF(4) and the d-U(600)(n)LiBF(4) electrolyte systems (250 degrees C and 243 degrees C, respectively). Electrochromic devices assembled with d-U(900)(n)LiBF(4) and d-U(600)(n)LiBF(4) electrolytes with compositions of 20 <= n <= 35 presented good color contrast, a maximum optical density of 0.23 and an encouraging performance in the coloring/bleaching process. The average transmittance in the visible region of the spectrum was above 74% for all the bleached samples analyzed.