Abstract We investigated annealing effects of La1−xSrxMnO3 (x = 0–0.6) on electrical resistivity and the temperature coefficient of resistivity (TCR). The annealed samples’ resistivity was lower than those of non-annealed samples. For example, annealing changed the resistivity of x = 0.3 at 25 °C from 4.50 × 10−5 to 3.71 × 10−5 Ω m. Remarkable difference in TCR was observed after annealing, for x = 0.3, 0.45, and 0.5. For x = 0.3, the TCR after annealing was 4000 ppm/°C, which was 1250 ppm/°C greater than that before annealing. We investigated (1) crystal phase, (2) Mn average valence, (3) Mott insulator–metal transition temperature, and (4) microstructure. The microstructure was remarkably varied for annealed x = 0.3 and 0.5. The average grain size of the x = 0.3 increased from 1.60 up to 2.38 μm. Results show that annealing affects resistivity and TCR because of grain growth during annealing.