In some electroceramic materials, their unique electrical properties are due to potential barriers, i.e., double Schottky barriers (DSBs), formed at grain boundaries. So far, some researchers have revealed that the electrical properties of DSB are closely related to grain boundary characters, especially grain boundary coherency. For example, highly coherent boundary does not give PTCR or varistic property, while random types exhibit clear resistivity jump or abrupt current increment. Therefore, a concept of grain boundary design will be required for future device manufacturing, even in bulk materials. But it has not been clarified yet why the electron transport behaviors depend on them. In order to address this question, it is necessary to carry out a systematic experiment focusing on single grain boundaries using well-defined bicrystals.