Mesostructured titanium-oxo/polymer hybrids were obtained by using Ti16O16(OEt)32 (TS) clusters or by aging solutions of Ti alkoxides as precursors. Dendrimers or PEO-based surfactants were used as templating agents. Solids were characterised by XRD, TEM, FTIR and multinuclear liquid and solid (MAS) NMR spectroscopy. Two synthetic approaches are described. In the alkoxide-based systems, the control of the high reactivities of the Ti (IV) metal centers, is essential to obtain ordered mesophases. The assembly of nanobuilding blocks (ANBB) permits to circumvent this high reactivity by using pre-formed Ti-oxo entities. The use of versatile functionalised dendrimers permits to control the reactivity at the surface of the cluster, giving birth to novel ordered architectures.