The article discusses the evaluation of the perovskite material (La0.6Sr0.4)0.95Mn0.8Ga0.2O3−δ (LSMG6482) as a promising candidate for solar thermochemical hydrogen production. Through experimental analysis using techniques like thermogravimetric analysis and high-temperature water splitting simulations, LSMG6482 demonstrated high and stable oxygen exchange capacity under controlled redox cycling conditions. The study compared LSMG6482 with established water splitters like ceria and (La0.6Sr0.4)0.95MnxAl1–xO3−δ (LSMA) perovskites. Results showed that LSMG6482 surpassed benchmark materials in hydrogen yields, with H2 yields of 165.1 μmol g–1 and up to four times greater yields under specific oxidation conditions. Crystallographic analysis indicated some secondary phase growth in perovskite compositions, except for LSMA6482, without affecting H2 yields. The findings highlight the potential of LSMG6482 for sustainable hydrogen production and synthetic fuel precursors in solar-driven processes.