Existing and future display and non-display applications of thermotropic liquid crystals rely on the development of new mesogenic materials. Electrical measurements of such materials determine their suitability for a specific application. In the case of molecular liquid crystals, their direct current (DC) electrical conductivity is caused by inorganic and/or organic ions typically present in small quantities even in highly purified materials. Important information about ions in liquid crystals can be obtained by measuring their DC electrical conductivity. Available experimental reports indicate that evaluation of the DC electrical conductivity of liquid crystals is a very non-trivial task as there are many ambiguities. In this paper, we discuss how to eliminate ambiguities in electrical measurements of liquid crystals by considering interactions between ions and substrates of a liquid crystal cell. In addition, we analyze factors affecting a proper evaluation of DC electrical conductivity of advanced multifunctional materials composed of liquid crystals and nanoparticles.