A di-urethane cross-linked poly(oxyethylene)/silica hybrid matrix ], synthesized by the sol-gel process, was doped with lithium triflate (LiCF 3 SO 3 ) and the 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) ionic liquid. The asproduced xerogel film is amorphous, transparent, flexible, homogeneous, hydrophilic, and has low nanoscale surface roughness. It exhibits an ionic conductivity of 3.64 × 10 −6 and 5.00 × 10 −4 S cm −1 at 21 and 100 • C, respectively. This material was successfully tested as electrolyte in an electrochromic device (ECD) with the glass/ITO/a-WO 3 /d-Ut(600) 10 LiCF 3 SO 3 [Bmim]Cl/c-NiO/ITO/glass configuration, where a-WO 3 and c-NiO stand for amorphous tungsten oxide and crystalline nickel oxide, respectively. The device demonstrated attractive electro-optical performance: fast response times (1-2 s for coloring and 50 s for bleaching), good optical memory [loss of transmittance (T) of only 41% after 3 months, at 555 nm], four mode modulation [bright mode (+3.0 V, T = 77% at 555 nm), semi-bright mode (−1.0 V, T = 60% at 555 nm), dark mode (−1.5 V, T = 38 % at 555 nm), and very dark mode (−2.0 V, T = 11% and −2.5 V, T = 7% at 555 nm)], excellent cycling stability denoting improvement with time, and high coloration efficiency [CE in = −6727 cm 2 C −1 (32th cycle) and CE out = +2794 cm 2 C −1 (480th cycle), at 555 nm].