Liquid crystal devices such as displays, various tunable optical components, and sensors are becoming increasingly ubiquitous. Basic physical properties of liquid crystal materials can be controlled by external physical fields thus making liquid crystal devices dynamically reconfigurable. The tunability of liquid crystals offers exciting opportunities for the development of new applications, including advanced electronic and photonic devices, by merging the concepts of flat optics, tunable metasurfaces, nanoplasmonics, and soft matter biophotonics. As a rule, the tunability of liquid crystals is achieved by applying an electric field. This field reorients liquid crystals and changes their physical properties. Ions, typically present in liquid crystals in minute quantities, can alter the reorientation of liquid crystals through the well-known screening effect. Because the electrical conductivity of thermotropic liquid crystals is normally caused by ions, an understanding of sources of ion generation in liquid crystals is of utmost importance to existing and emerging technologies relying on such materials. That is why measurements of electrical conductivity of liquid crystals is a standard part of their material characterization. Measuring the electrical conductivity of liquid crystals is a very delicate process. In this paper, we discuss overlooked ionic phenomena caused by interactions of ions with substrates of the liquid crystal cells. These interactions affect the measured values of the DC electrical conductivity of liquid crystals and make them dependent on the cell thickness.