The electronic structure of titanium(IV) tert-butoxide Ti(OC(CH3)(3))(4) has been investigated by UV photoelectron spectroscopy (UPS) and DFT/OVGF calculations. This is the first reported UPS spectrum of a titanium alkoxide. We discuss the nature of metal-ligand bonding on the basis of empirical arguments. (c) 2006 Elsevier B.V. All rights reserved.