Cubic perovskite (CaTiO3) was successfully synthesized by a facile solvothermal method and was utilized to sequestrate U(VI) from aqueous solutions. The batch experiments revealed that carbonate inhibited U(VI) sequestration at pH > 6.0 due to the formation of uranyl-carbonate complexes. The maximum sequestration capacity of U(VI) on perovskite was 119.3 mg/g (pH 5.5). The sequestration mechanism of U(VI) on perovskite were investigated by XPS and EXAFS techniques. According to XPS analysis, the presence of U(IV) and U(VI) oxidation states revealed the photocatalytic reduction of U(VI) by perovskite under UV-vis irradiation. In addition, photocatalytic reduction performance significantly decreased in the presence of carbonate. Based on EXAFS analysis, the occurrence of U-Ti and U-U shells revealed the inner-sphere surface complexation and reductive precipitation of U(VI) on perovskite. These findings herein are crucial for the application of perovskite-based composites in the decontamination of U(VI) in aquatic environmental cleanup.