Abstract La (0.9− x) Ce x FeO 3 perovskite-like catalysts were investigated for the production of hydrogen from simulated coal-derived syngas via the water–gas shift reaction in the temperature range 450–600 °C and at 1 atm. These catalysts exhibited higher activity at high temperatures ( T ≥ 550 °C), compared to that of a commercial high temperature iron–chromium catalyst at 450 °C. Addition of a low Ce content ( x = 0.2), has little influence on the formation of the LaFeO 3 perovskite structure, but enhances catalytic activity especially at high temperatures with 19.17% CO conversion at 550 °C and 40.37% CO conversion at 600 °C. The LaFeO 3 perovskite structure and CeO 2 redox properties play an important role in enhancing the water-gas shift activity. Addition of a high Ce content ( x = 0.6) inhibits the formation of the LaFeO 3 perovskite structure and decreases catalyst activity.