The NaBiO3 nano-sheets were syntheized by a facile method of oxidizing Bi3+ in alkaline solution. The as-syntheized products were used to adsorb Ce3+ in solution and characterized by XRD, SEM, TEM and XPS. The results show that the synthized products have nano-sheets structure with a size of ~50 nm and high selective adsorption performance on Ce3+. After adsorbtion of Ce3+, all Na cations in NaBiO3 nano-sheets have been fully exchanged and replaced by Ce cations and the chemical state of Ce and Bi were Ce4+ and Bi3+ in the generated products. The XPS analysis shows that Bi5+ species were changed into Bi3+ species in the adsorbtion process of Ce3+. So the adsorption process of Ce3+ contains two process of the ion-exchange between Ce3+ and Na+ cations and the oxidation of Ce3+ species, and the selective adsorption process of Ce3+ ion was achieved by an ion-exchange and redox reaction process.