A unique titanium oxo cluster with a ferrocene ligand was synthesized and characterized by single crystal X-ray analysis. Six ferrocene carboxylates coordinate to a D-3d Ti6O6 core to be a redox active cluster 1, [Ti6O6((OPr)-Pr-i)(6)(O(2)CFc)(6)]. An analogue 2, [Ti6O6((OPr)-Pr-i)(6)((O2CBu)-Bu-i)(6)], where the redox active ferrocene group is replaced by isobutyrate, is also reported as a contrast. The six ferrocene moieties in 1 are structurally identical to give a main redox wave at E-1/2 = 0.62 V in dichloromethane investigated by cyclic voltammetry. Photocurrent responses using electrodes of clusters 1 and 2 were studied, and the response properties of 1 are better than those of 2. The electronic spectra and theoretical calculations indicate that charge transfer,occurs from ferrocene to Ti(IV) in 1, and the presence of the ferrocene moiety gives efficient electron excitation and charge separation. Cluster 1 is a cooperative system of TiO duster and redox active ferrocene. Photocurrent response properties of an electrode of I for four saccharides, glucose, fructose, maltose, and sucrose, were tested, and only reducing sugars were responsive. The electrode of 2 is also photocurrent responsive to saccharides, but the current densities are lower than those of redox active I.