Ce1−xPrxO2−δ (x=0, 0.05, 0.1, 0.2 and 0.3), as reactive ceramics synthesized by combustion method for H2 production via two-step water splitting reaction with concentrated solar energy, was investigated in present work. XRD analysis of the samples shows that Pr6O11 underwent a phase transition into Pr2O3and Pr2O3 cannot be oxidized by steam to yield H2 in two-step water splitting reaction. The solid solutions of the samples containing Ce were formed with a single cubic CeO2 fluorite structure after synthesis and even after two-step water splitting reaction. Although Pr cannot be oxidized by steam to generate H2 in two-step water splitting reaction, the promotion effect is present with the introduction of 5mol% and 10mol% Pr into CeO2 on the amounts of O2 and H2, but the volume of H2 evolved is enhanced or not, strongly dependent on the H2-generation temperature. The optimum H2-generation temperature is 1023K.