The imidazole-based ligands, bis(imidazol-1-yl) methane (Bizm, 1a) and (pyrenyl) bis(imidazol-1-yl) methane (Pbizm, 2a) were prepared. With LiClO4, these two compounds formed two novel organic-inorganic hybrid materials: a 3D network polymer Li(Bizm)center dot ClO4 (1b) and a 1D chain polymer Li(Pbizm)(2)center dot ClO4 (2b). The intriguing topological and physiochemical characteristics of 1b and 2b are reported on the basis of the X-ray single-crystal structure analysis and Li ion binding studies.