The physical properties of a liquid crystal–ionic liquid system were investigated. Low-frequency dielectric spectroscopy for 4-cyano-4′-pentylbiphenyl (5CB) doped with 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4) for the nematic and isotropic phase of host substances was performed. We obtained electrical conductivity values in the range from 298.2 K to 313.2 K and the conductivity anisotropy was confirmed. Further study of the relaxation process for bmim+ allowed us to extract the relaxation frequencies and amplitudes from experimental data and confirm the temperature scaling; the thickness of the interfacial layers was estimated for the homogeneous and homeotropic alignments of the prepared composite. An attempt to unfold the ion contribution on the charge transport was made in order to better understand the electrode polarization process. In this work, the influence of the alignment layer and phase state on the interfacial layer formation in liquid crystal media will be explained better.