Two characterization techniques, the steady-state Conduction Current (CC) and the low frequency Dielectric Spectroscopy (DS) are reviewed and compared to each other in order to choose the most suitable method for evaluating the static electrical conductivity (σDC) of an insulating material. In the case of polymeric materials operating above 200°C, the DS appears as being better suited. These techniques are applied for insulating materials identified as good candidates for high temperature (HT) applications and new results are presented. HT polyimide, parylene films and silicon nitride substrates are studied. These examples highlight the σDC magnitudes for temperatures up to 400 °C, as well as other relevant parameters to be taken into account for practical applications.