The titanium oxo-organo clusters [Ti16O16(OEt)32] are used as precondensed building blocks for the sol-gel synthesis of titanium oxide nanostructures in the presence of an amphiphilic block copolymer PS-b-PMAA (PS = polystyrene block; PMAA = polymethacrylic acid block) as a structure directing agent. It is shown that clusters—opposite to the more reactive titanium alkoxides—can be organized and hydrolysed under controlled conditions. The resulting polymer-titanium oxide nanocomposites were characterised by TEM, SAXS, 17O MAS NMR spectroscopy.