The effects of different sintering temperatures on the system of Ba0.5Sr0.5TiO3-La0.8Ca0.2MnO3 (BST-LCM) material were investigated by means of scanning electron microscopy, X-ray, resistance-temperature measurements, and X-ray photoelectron spectroscopy. X-ray diffraction and X-ray photoelectron spectroscopy confirm that BST-LCM is completely miscible and BST is the main phase, which under the premise of following the theory of small polaron conduction, titanium ions interact with manganese ions, which affects the electrical properties of the system of BST-LCM material. For the electrical properties of related, the LCM content is inversely proportional to the activation energy. Through the linear fitting of the experimental data, the empirical formula between the sintering temperature B value and the content of solid solution is obtained, and the approximate B value within a certain range can be preliminarily calculated.