When electrical characterization of thin conductive coating is carried out, it requires an effective electrode configuration that prevents design problems due to low thickness, such as short circuits or electrode diffusion. In this work, two electrode configurations were carried out, surface and volume configurations, in order to compare and demonstrate the efficiency of surface electrode configuration for thin films. Highly conductive coatings based on carbon black (CB) have been prepared by the sol–gel method, and electrical properties were measured for both configurations, indicating that when the thickness of the film is low enough, the electrical conduction with the electrodes disposed on the surface is produced for the entire volume. This effect facilitates the design and treatment of the coating. This configuration could be very useful for many technological applications.