Highly anisotropic TiO2 nanostructures (see Figure) of several hundreds of nanometers in length were obtained by oriented assembly of preformed TiO2 nanoparticles with typical diameters of 5 nm. The assembly is directed by a particularly small amount of a polydentate ligand with a low molecular weight, which binds selectively to specific crystal faces of the titania nanoparticles.