Combining partial oxidation of methane with H2O/CO2 splitting under solar thermal conditions presents a very promising strategy for producing solar fuels. In order to achieve this, the development of stable and efficient redox catalysts is necessary, among which ceria (CeO2) seems to be one of the most promising for lattice oxygen transfer. In this study, CeO2 was used for splitting CO2 and H2O using concentrated solar energy with reaction temperatures in the range 900-1100 degrees C. The experimental studies in a solar-driven thermogravimetric system indicated that both CH4 induced reduction and CO2 induced oxidation of CeO2-delta followed close reaction orders with activation energies of 109 and 36 kJ mol t, respectively. The results were compared with those obtained from hydrothermal templating and surfactant induced self-assembly. To our knowledge, such materials are studied for the first time for CH4 induced fuel production via solar thermochemical redox cycles. Enhanced reaction rates and stability upon cycling were observed for materials synthesized by hydrothermal and self-assembly methods. Experiments were also carried out to deduce the effect of various inert materials (MgO and A1203) as promotional agents. Higher reduction rate and maximum nonstoichiometry (delta = 0.431) during reduction at 1000 degrees C were observed in the case of MgO promoted CeO2. In addition, the amount of evolved CO was found to be the highest (delta = 0.402), indicating almost complete reoxidation. The achieved nonstoichiometry and the resulting fuel productivity are more than 10 times higher than the reported values for thermal reduction of ceria. Studies were also performed in a solar reactor prototype, enabling both partial ceria reduction with methane, followed by oxidation with H2O/CO2. Typically, MgO and Al2O3 promoted ceria were tested under packed bed conditions and compared with commercial ceria for syngas production. In this case, significant enhancement in the system efficiency was observed for MgO promoted CeO2.