AbstractPerovskite oxides have recently been proposed as promising redox intermediates for solar thermochemical splitting of H2O and CO2, offering the benefit of significantly reduced operating temperatures. We present a systematic experimental screening of doped lanthanum manganites within the composition space La1−x(Ca,Sr)xMn1−yAlyO3 and identify several promising redox materials. In particular, La0.6Sr0.4Mn0.6Al0.4O3 and La0.6Ca0.4Mn0.6Al0.4O3 boast a five‐ to thirteen‐fold improvement in the reduction extent compared to the state‐of‐the‐art material CeO2 in the temperature range 1200–1400 °C. The materials are shown to be capable of splitting CO2 into CO fuel when isothermally cycled between low‐pO2 and high‐pCO2 environments at 1240 °C and to approach full reoxidation in CO2 with temperature swings as low as 200 °C, with mass‐specific fuel yields up to ten times that of CeO2. The underlying material thermodynamics are investigated and used to explain the favorable redox behavior.