Layered titanates (Na2Ti3O7·nH2O) with exchangeable sodium cations located in the interlayer have been synthesized by simple hydrothermal treatment of Ti precursor in concentrated NaOH solutions. By proper control of the synthesis conditions, different morphologies of nanofibers and nanosheets are obtained. The metastable layered structure of the titanates collapses during the ion exchange, resulting in irreversible ion exchange. Target cations (eg., Ag+, Cu2+, Pb2+ and Eu3+) are completely concentrated from water and then tightly immobilized in the interlayer which is of great significance for the removal and subsequent safe disposal of hazardous metal cations. The ion exchange of the nanosheets is much more efficient than that of the nanofibers and other inorganic ion exchangers due to the larger surface area, less stable layered structure and larger amount of interlayer water of the nanosheets. The ion exchange of the titanates is also very selective. Valence, hardness, and radius of cations are main factors affecting the selectivity. Cations trapped in the interlayer are released by an acid-induced phase transformation of the titanate nanosheets to rutile. Then the rutile can be used as a new Ti precursor to synthesize the titanate nanostructures, resulting in a full cycle of material use. The nanosheets may find applications in the decontamination and safe disposal of radioactive and heavy metal cations and also in the collection of valuable cations from water.