By using the extreme-ultraviolet laser in Artemis, CLF, we employed a measurement involving UV-pump and extreme-ultraviolet photoelectron spectroscopy on a rutile TiO2(110) surface. We studied the influence of inter-band excitation of TiO2 on the resulting chemical state of Ti and O as monitored by shallow core-levels as well as the valence band. This is of great importance in understanding the flow of energy and charge transfer at the TiO2 surface in photocatalytic processes.