Hollow microspheres of titanium dioxide have been prepared by spray-drying a colloidal suspension of an exfoliated titanate followed by heating above 400 degrees C. The individual hollow sphere with a diameter of tens of micrometers is characterized by its extremely thin crust, tens of nanometers thick. Because 99% of the particle volume is empty, the powder is very light with an apparent density of similar to 0.02 g cm(-3). These microspheres can be converted into thin flaky particulates of TiO2 by gentle milling.