Rattle-type TiO2@void@SiO2 particles, with commercial TiO2 particles encapsulated into hollow SiO2 shell, were fabricated by successive coating of multilayer polyelectrolytes and SiO2 shell onto TiO2 particles and then treatment by UV irradiation to remove the polyelectrolyte layers. TEM observation showed that the composite particles had a unique rattle-type structure in which there existed void space between TiO2 core and SiO2 shell. The photocatalytic degradation of Rhodamine B indicated that these composite particles with larger void space tended to have higher photoactivity. The polyurethane films doped with rattle-type TiO2@void@SiO2 composite particles had very good UV-shielding property.