Perovskite material is one of the promising classes of redox catalysts for hydrogen production through two-step thermochemical H2O splitting. Herein, an analogue of La1−xCa x MnO3 perovskite was systematically investigated as a catalyst for thermochemical H2 evolution. The Ca doping level (x = 0.2, 0.4, 0.6, 0.8) and re-oxidation temperature were comprehensively optimized for the improvement of catalytic performance. According to our experimental results, La0.6Ca0.4MnO3 perovskite displayed the highest yield of H2 at the re-oxidation temperature of 900 °C and the obtained H2 production was ~ 10 times higher than that of the benchmark ceria catalyst under the same experimental condition. More importantly, La0.6Ca0.4MnO3 perovskite catalyst exhibited impressive cyclic stability in repetitive O2 and H2 test.