This study focuses on the use of cerium-based mixed oxides for hydrogen production by solar-driven thermochemical two-step water-splitting. Mixed cerium oxides are proposed in order to decrease the reduction temperature of ceria and to avoid material sublimation occurring above 2,000 °C during the high-temperature solar step. Ceria-based nanopowders were synthesized by soft chemistry methods including the modified Pechini method. The influence of the synthesis method, the type of cationic element mixed with cerium, and the content of this added element was investigated by comparing the reduction temperatures of the derived materials. The synthesized powders were characterized by X-ray diffraction, thermogravimetric analysis, SEM, and Raman spectroscopy. Results showed that the synthesized pure cerium oxide is more reactive toward reduction than a commercial powder. Among the different elements added to ceria that were screened, the addition of zirconium significantly improved the reduction of ceria at temperatures below 1,500 °C. Increasing zirconium content further favored cerium reduction yield up to 70%. Water-splitting tests were performed to demonstrate the reactivity of the developed materials for H2 production. The amount of H2 evolved was enhanced with a temperature increase, the maximum H2 production from Ce0.75Zr0.25O2−δ was 0.24 mmol/g at 1,045 °C, and the powder reactivity upon cycling was demonstrated via thermogravimetry through two successive reduction–hydrolysis reactions.