During solvothermal alcoholysis of a mixture of TiI4 and Ti((OPr)-Pr-i)(4), a {I@Ti-22} cage cluster encapsulating an OH and iodide guests is crystallized. The {I@Ti-22} host-guest duster surface is postfunctionalizable with catecholate and carboxylate ligands. The synthetic details; structural characterization, spectroscopic properties of the obtained cages clusters are provided. The present study provides candidates for modeling ligand exchange and electron-hole transfer at the titanate nanopartide surface, and meanwhile offers new opportunities for understanding the TiO2 nanocrystalline formation in solvothermal processes.