In line with the development of electronic devices and technologies, the demand for improving ferroelectric materials’ performance is increasing. Since K0.5Na0.5NbO3 (KNN), an eco-friendly ferroelectric material that does not use lead and has a high Curie temperature, it is attracting attention to its usability as a high-temperature dielectric, and various studies are being conducted to increase performance. In a KNN having a perovskite structure, there was a simulation result that the KNN has higher spontaneous polarization when the A-site in which sodium ions exist is replaced with lithium ions. If the simulation results can be proven experimentally, the application range of KNN-based ferroelectric materials will increase. To this end, we tried to manufacture a K1-xLixNbO3 (KLN) with high electrical characteristics by fabricating niobium-deficient and potassium-excessive compositions, which attempt was made to solve the stoichiometry problem by volatilization and suppress secondary phases. If KLN’s secondary phase suppression and relative permittivity improvement are successful, it will contribute to meeting the demand for developing electronic devices.