To investigate the conduction properties of ionic liquid crystal electrolytes and to correlate them to their molecular structure, two electrolytes based on imidazolium iodides have been chosen for a comparative study: one ionic liquid crystal (1-dodecyl-3-methylimidazolium iodide) (C12) and one ionic liquid (1-hexyl-3-methylimidazolium iodide) (C6). For the electrical characterization of the samples the electrochemical impedance spectroscopy technique (EIS) has been used in the frequency range 1MHz ÷ 10mHz. For both electrolytes three frequency domains have been singled out. At large frequencies a hopping mechanism ensures the relative high conductivity of ionic liquids. A good fit of the conductivity data with respect to temperature with a Vogel-Tamman-Fulcher (VTF) equation has been done. The interesting result is that although C12 has a higher viscosity than C6 and thus a smaller conductivity was expected the observed conductivity is actually larger, this fact being attributed to the smectic A liquid crystal order of C12. At medium frequencies and especially at low frequencies the buildup of double layers by the electrodes is well observed. Assuming that in this region (10Hz ÷ 10mHz) the cell is equivalent to an electric circuit formed by the parallel of a resistance, R0, and a capacitance, C0, the simple Debye relaxation model, characterized by one relaxation time, has been modified taking into account the adsorption phenomenon in the Langmuir approximation. A theoretical interpretation of the experimental results based on the double layer model is presented.