Na1-xLixNbO3 ceramics (for x = 0.08, 0.1, 0.2) were fabricated by the conventional solid state reaction method. The influence of LiNbO3 on the microstructure, electric, thermal properties of Na1-xLixNbO3 ceramics was studied and a significant influence of doped Li ions on the electrical properties was observed. The electrical properties were improved and are described as the best for x = 0.1 (near a morphotropic phase boundary) Na1–xLixNbO3 solid solutions. After crossing the morphotropic phase boundary for x = 0.2, the electric properties are getting worse. These types of solid compounds show some interesting properties suitable for practical applications.