Patterned "bead in pore" composite film with hemispherical or mushroomlike TiO2 microparticles lying in the holes of a honeycomblike polystyrene matrix has been fabricated by a template-free bottom-up approach from a homogeneous solution of TiCl4/polystyrene/CHCl3 using the breath figures method. It is a very simple way to prepare hemispherical or mushroomlike TiO2 microparticles and to get the hexagonally nonclose-packed arrays of asymmetrical particles with or without polymer matrix, which have potential applications in photonics.