The electrical conductivity was provided to structural ceramics by controlling the grain boundary phase. We focused on the grain boundary phase of Si3N4 ceramics, which can be considered as an infinite network for conducting paths. In this study, we investigated the correlationship of the microstructure, mechanical properties, and electrical conductivity of Si3N4 ceramics with V2O5 based glasses. The Si3N4 ceramic with V2O5 based glasses were successfully fabricated by controlling the composition of grain boundary phase. Fabricated materials by a PECS method indicated a very fine microstructure. The mechanical properties of Si3N4 ceramics with V2O5 based glasses were not good compared to those of conventional Si3N4. However, the values for the SNVB and the SNVBA were four or six orders of magnitude higher at room temperature and had excellent mechanical properties compared to pure V2O5 based glasses.