Layered titanate Na2Ti3O7 powders with varying sizes were prepared by solid-state reaction of Na2CO3 and TiO2 with different average particle sizes. The structures of the titanates and the products which had undergone H+ and Ag+ exchange were investigated by XRD, TEM and BET analysis. The influence of the particle size of starting material TiO2 on the reaction rate, the particle size and ion-exchange property of the resulting products was studied. It is found that nanometer sized TiO2 facilitates the solid-state reaction and leads to the formation of ultrafine titanate. The H+-exchange property is improved by decreasing the particle size of Na2Ti3O7 and the small sized layered titanate can be exfoliated easily by AgNO3 solution. (C) 2003 Kluwer Academic Publishers.