Thermochemical splitting of CO2 and H2O via two-step metal oxide redox cycles offers a promising approach to produce solar fuels. Perovskite-type oxides with the general formula ABO3 have recently gained attention as an attractive redox material alternative to the state-of-the-art ceria, due to their high structural and thermodynamic tunability. A novel Ce-substituted lanthanum strontium manganite perovskite-oxide composite, La3+0.48Sr2+0.52(Ce4+0.06Mn3+0.79)O2.55 (LSC25M75) is introduced, aiming to bridge the gap between ceria and perovskite oxide-based materials by overcoming their individual thermodynamic constraints. Thermochemical CO2 splitting redox cyclability of LSC25M75 evaluated with a thermogravimetric analyzer and an infrared furnace reactor over 100 consecutive redox cycles demonstrates a twofold higher conversion extent to CO than one of the best Mn-based perovskite oxides, La0.60Sr0.40MnO3. Based on complementary in situ high temperature neutron, synchrotron X-ray, and electron diffraction experiments, unprecedented structural and mechanistic insight is obtained into thermochemical perovskite oxide materials. A novel CO2 splitting reaction mechanism is presented, involving reversible temperature induced phase transitions from the n = 1 Ruddlesden–Popper phase (Sr1.10La0.64Ce0.26)MnO3.88 (I4/mmm, K2NiF4-type) at reduction temperature (1350 °C) to the n = 2 Ruddlesden–Popper phase (Sr2.60La0.22Ce0.18)Mn2O6.6 (I4/mmm, Sr3Ti2O7-type) at re-oxidation temperature (1000 °C) after the CO2 splitting step.