This work reports on the development of a transient heat transfer model of a solar receiver–reactor designed for thermochemical redox cycling by temperature and pressure swing of pure cerium dioxide in the form of a reticulated porous ceramic (RPC). In the first, endothermal step, the cerium dioxide RPC is directly heated with concentrated solar radiation to 1500 °C while under vacuum pressure of less than 10 mbar, thereby releasing oxygen from its crystal lattice. In the subsequent, exothermic step, the reactor is repressurized with carbon dioxide as it cools, and at temperatures below 1000 °C, the partially reduced cerium dioxide is re-oxidized with a flow of carbon dioxide. To analyze the performance of the solar reactor and to gain insight into improved design and operational conditions, a transient heat transfer model of the solar reactor for a solar radiative input power of 50 kW during the reduction step was developed and implemented in ANSYS cfx. The numerical model couples the incoming concentrated solar radiation using Monte Carlo ray tracing, incorporates the reduction chemistry by assuming thermodynamic equilibrium, and accounts for internal radiation heat transfer inside the porous ceria by applying effective heat transfer properties. The model was experimentally validated using data acquired in a high-flux solar simulator (HFSS), where temperature evolution and oxygen production results from model and experiment agreed well. The numerical results indicate the prominent influence of solar radiative input power, where increasing it substantially reduces reduction time of the cerium dioxide structure. Consequently, the model predicts a solar-to-fuel energy conversion efficiency of >6% at a solar radiative power input of 50 kW; efficiency >10% can be obtained provided the RPC macroporosity is substantially increased, and better volumetric absorption and uniform heating is achieved. Managing the ceria surface temperature during reduction to avoid sublimation is a critical design consideration for direct absorption solar receiver–reactors.