Whereas a large number of sensitized polyoxotitanate clusters have been reported, information on the electrochemical properties of the fully structurally defined nanoparticles is not available. Bridging of this gap will allow a systematic analysis of the relation between sensitizer-cluster binding geometry, electronic structure and electron injection properties. Ti17O28(O(i)Pr)16(Fe(II)Phen)2 is a member of a doubly-doped series of nanoclusters in which the phenanthroline is attached to the surface-located transition metal atom. The visible spectrum of a dichloromethane solution of the studied sample shows a series of absorption bands in the 400-900 nm region. Theoretical DOS and TDDFT calculations indicate that the bands in increasing wavelength order correspond essentially to metal-to-core charge transfer (MCCT) at ∼460 nm, metal-to-ligand charge transfer (MLCT) at ∼520 nm and d-d metal-atom transitions. Exposure of a thin layer of the sample to light in a photoelectrochemical cell produces an electric current in the 400 to ∼640 nm region. The fit of the wavelength range of the electron injection with the results of the calculations suggests that charge injection into the FTO anode occurs both from the TiO cluster and from the phenanthroline ligand. Injection from the phenanthroline via the cluster orbitals is ruled out by the lower energy of the phenanthroline orbitals.