Since 2006, ceria is used as a redox reactive material for production of H-2, CO, and syngas via a two-step solar driven thermochemical H2O/CO2 splitting cycle. Different forms of phase pure ceria were studied over a wide range of temperatures and oxygen partial pressures. To increase the redox reactivity and long-term stability, the effects of incorporation of different dopants in to the ceria fluorite structure (in varying proportions) were studied in detail. A variety of solar reactors, loaded with ceria based ceramics, were designed and developed to investigate the performance of these materials towards thermal reduction and H2O/CO2 splitting reactions. The thermodynamics and reaction kinetics of ceria based solar thermochemical H2O/CO2 splitting cycles were also explored heavily. This paper presents a detailed chronological insight into the development of ceria-based oxides as reactive materials for solar fuel production via thermochemical redox H2O/CO2 splitting cycles. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.