Porous hollow nanostructures have attracted intensive interest owing to their unique structure and promising applications in various fields. A facile hydrothermal synthesis has been developed to prepare porous hollow nanostructures of silicate materials through a sacrificial-templating process. The key factors, such as the concentration of the free metal cation and the alkalinity of the solution, are discussed. Porous hollow nanostructures of magnesium silicate, nickel silicate, and iron silicate have been successfully prepared by using SiO(2) spheres as the template, as well as a silicon source. Several yolk-shell structures have also been fabricated by a similar process that uses silica-coated composite particles as a template. As-prepared mesoporous magnesium silicate hollow spheres showed an excellent ability to remove Pb(2+) ions in water treatment owing to their large specific surface and unique structures.