The solidstate sintering method was picked to prepare the BaLaxBi1-xO3 family materials. The microscopic configurations and phases of the samples were analyzed in depth by XRD and SEM technologies. By reviewing the analysis, it is found that the samples in the experiments form a single solid solution after calcination, and the grain cell boundaries appear to be more distinguishable and the coarseness of the grain tend to be more event. Also, the grain boundaries become more compacted when the temperature of the sintering hikes up. The experimental results show that the sample exhibits NTC characteristics in a specific temperature range; the suitable calcination temperature range is 800~900 ℃, and the optimal sintering temperature range is 1 050~1 100 ℃; the value of material constant Bis reduced from 3 629 K at 990 ℃ to 3 300 K at 1 050 ℃, and the resistivity ρ is reduced from 1 103 Ω·cm to 166 Ω·cm.