Montmorillonites are composed of alummosilicate layers stacked one above the other, and the layer thickness is approximately 1 nm. In this work lithium modified montmorillonite (Li-MMT) was prepared and used as a lithium macro-anion salt in gel electrolytes. It was found that Li-MMT exhibited good compatibility with poly(ethylene glycol), DMSO and the ionic liquid, 1-ethyl-3-methylimidazolium dicyanamide (EMIdca), and a few of novel gel electrolytes based on Li-MMT were obtained. These gel electrolytes were investigated by X-ray powder diffraction, solid state NMR, conductivity measurements and cyclic voltammetry. High conductivities up to 10(-4) to 10(-3) S/cm at room temperature were observed with these macro-anion gel electrolytes. These gel materials were promising to be used as lithium conductive electrolytes in electrochemical devices, such as lithium batteries. (C) 2007 Elsevier B.V, All rights reserved.