Film thermocouples as the most effective tool are used to monitor the real‐time and accurate in situ temperature in harsh environment, which will demand their electrodes with high thermal‐resistant properties, high sensitivity, and stability. In this work, a series of solid solutions based on strontium lanthanum chromate were systematically investigated as new electrodes. LaCrO3 and La0.8Sr0.2CrO3 with some glass additives were chosen to fabricate high‐performance thick‐film thermocouple due to a bigger Fermi level difference between them. The thermocouple shows a high sensitivity (107.8 μV/°C) during static calibration, and an excellent reproducibility and stability during multicycle calibrations carried out up to 1550°C, resulting in a record ultra‐high temperature sensing in film thermocouples. This facile thermocouple may open up a new way to measure high temperature in air or oxidation atmosphere accurately.