The fabrication of monodispersed hollow spheres in varying sizes and shapes is very interesting and has a lot of potential applications. This paper provides a very simple route to preparing hollow titania spheres using polystyrene (PS) as a template. In this approach, the titania shells were first formed and the PS cores were dissolved subsequently, even synchronously, in the same medium; neither an additional dissolution nor a calcination process was needed to remove the PS cores. Transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and Barret-Emmet-Teller measurements were used to characterize the monodispersed hollow titania spheres. A possible formation mechanism of the hollow spheres was proposed.