The effects of additives of poly(methyl methacrylate) (PMMA) and HAuCl4 on the morphologies of hybrid titania films formed via co-assembly of polystyrene-block-poly (ethylene oxide) (PS-b-PEO) copolymers, titania sol-gel precursor in a selective solvent were investigated. The results show that addition of PMMA or HAuCl4 has an important influence on the morphologies of hybrid titania films. Addition of PMMA or HAuCl4 can induce the morphology transition of the PS-b-PEO/titania sol-gel mixture from spherical micelles to vesicles. Therefore, the morphologies of the hybrid films formed on silicon substrate surfaces by spin-coating can be controlled by the addition of homopolymer (PMMA) or inorganic precursor (HAuCl4) into the PS-b-PEO/titania sol-gel mixtures, allowing access to nanoparticles or nanoporous films. After removing the polymer matrix, nanoparticle aggregates or nanobowl-like structures are left behind on the substrate surfaces. (C) 2008 Elsevier Ltd. All rights reserved.