After pioneering attempts for the introduction of graph theory in the field of ceramics and microstructures, where 1D and 2D graphs were used, in this paper we applied 3D graphs for the breakdown voltage calculation in BaTiO3 sample with some predefined constraints. We have described the relations between grains in the sample and established a mathematical approach for the calculation of breakdown voltage using experimental results. As a result, we introduced mapping between the property of sample and grain structure, then between the grain structure and mathematical graph, using various crystal structures. The main idea was to apply 3D graph theory for the distribution of electronic parameters between the neighboring grains. With this study, we successfully confirmed the possibilities for applications of graphs as a tool for the determination of properties even at the intergranular level.