This report presents detailed studies on the elemental analysis, vibrational spectroscopy, thermal stability and electrical spectroscopy of two new hybrid inorganic-organic polymers which have been synthesised by a sol-gel method using glycerol and zirconium(IV) butoxide as precursors. These materials have been doped by means of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm-TFSI) ionic liquid (IL), which is insoluble in water. The elemental composition of the obtained polymers [Zr(C6O5H11)] (1) and [Zr(C11O4H31)] (2) has been determined by CHN analysis and by ICP-AES measurements. FT-IR and FT-Raman spectroscopy investigations have been performed to study the molecular structure of the polymers and the interactions of EMIm-TFSI with the host networks. Differential scanning calorimetry measurements show the presence of at least one glass transition temperature (T-g) in both 1 and 2 materials. The broadband dielectric spectroscopic measurements have been carried out between 10(-2) Hz to 10 MHz from -100 degrees C to 100 degrees C with a 5 degrees C step. The conductivities of the polymers 1 and 2 have been found to be in the order of 10(-8) to 10(-11) S cm(-1) at 25 degrees C, so they can be defined as dielectric materials. After doping 2 with EMIm-TFSI, the conductivity at 25 degrees C of the obtained complex [Zr(C11O4H31)](15)/(EMIm-TFSI) (2') increased three orders of magnitude resulting ca. 10(-5) S cm(-1). The permittivity spectra revealed two relaxation bands which were attributed to the alpha relaxation modes of the polymer networks. (C) 2009 Published by Elsevier B.V.