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This study is the first to quantify energy band alignments at a nanostructured TiO2/Au22(SG)18 cluster interface using X-ray photoelectron spectroscopy. The d-band of Au clusters shows band-like character and occupied states at the Fermi level are not detected. The results provide evidence of the existence of a finite optical energy gap in Au22(SG)18 clusters and the molecular-like nature of these clusters. The pinning position of the Fermi energy level at the interface was determined to be 2.8 and 1.3 eV higher than the top of the TiO2
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