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In this contribution we study experimentally the electronic properties of nanocrystalline FeNiTi alloy thin lms using X-ray photoelectron spectroscopy. The structure of the samples has been studied by X-ray diraction. Their bulk chemical compositions were measured using X-ray uorescence method. The surface chemical composition and the cleanness of all samples were checked in situ, immediately after deposition, transferring the samples to an UHV analysis chamber equipped with X-ray photoelectron spectroscopy. X-ray diraction studies revealed the formation of nanocrystalline FeNiTi alloy thin lms at a substrate temperature of about 293 K. In situ X-ray photoelectron spectroscopy studies showed that the valence bands of nanocrystalline samples are broader compared to those measured for the polycrystalline bulk alloys. Such modications of the valence bands of the nanocrystalline alloy thin lms could inuence on their hydrogenation properties.