The reaction of titanium(IV) chloride with sodium hexafluoroisopropoxide, carried out in hexafluoroisopropanol, produces titanium(IV) hexafluoroisopropoxide, which is a liquid at room temperature. Recrystallization from coordinating solvents, such as acetonitrile or tetrahydrofuran, results in the formation of bis-solvate complexes. These compounds are of interest as possible Ziegler-Natta polymerization catalysts. The acetonitrile complex had been structurally characterized previously and adopts a distorted octahedral structure in which the nitrile ligands adopt a cis configuration, with nitrogen lone pairs coordinated to the metal. The low-melting tetrahydrofuran complex has not provided crystals suitable for single-crystal X-ray analysis. However, the structure of chloridotris(hexafluoroisopropoxido-κO)bis(tetrahydrofuran-κO)titanium(IV), [Ti(C 3 HF 6 O) 3 Cl(C 4 H 8 O) 2 ], has been obtained and adopts a distorted octahedral coordination geometry, with a facial arrangement of the alkoxide ligands and adjacent tetrahydrofuran ligands, coordinated by way of metal-oxygen polar coordinate interactions.