Abstract Polymer microspheres stabilized by titania nanoparticles were synthesized using a two-step Pickering emulsion polymerization process, in which nanosized titania nanoparticles were used as solid emulsifiers and building blocks. It gives a simple but novel route for the fabrication of functional inorganic/polymer hybrid materials with controlled microstructures. The final Pickering emulsion can be applied to various substrates forming continuous films with highly ordered nanosized to microsized TiO 2 protuberances across the films. Those films will have potential applications for photo-catalyst, water and air purification.