Ionic liquid of [BMIM][BF4] based sol-gel modified electrode ([BMIM][BF4]/Gel/Au electrode) was prepared by immobilization of [BMIM][BF4] into silica sol-gel matrix on the surface of An electrode via a simple sol-gel method. Taking advantage of ion exchange reaction between [BMIM][BF4] and K3Fe(CN)(6), Fe(CN)(6)(3-) was entrapped into the sol-gel matrix when [BMIM][BF4]Gel/Au electrode was immersed in K3Fe(CN)(6) solution. Following by continuously scans, the cyclic voltammograms of the resulting [BMIM](3)Fe(CN)(6)/ Gel/Au electrode in K3Fe(CN)(6) solution behaved "PB (Prussian Blue)-growing pattern". FTIR, elemental analysis and UV-Vis absorbance spectra results manifested the formation of PB in the sol-gel matrix. Furthermore, the formation mechanism, kinetics and stability of the PB/Gel/Au electrode formed by this method were discussed. (C) 2007 Elsevier B.V. All rights reserved.