In this paper, we study the formation of TSe2 (T = Ta, Ti)-layered compound thin films, grown on polycrystalline Ta substrates. The experiments were performed in UHV by means of photoemission spectroscopy with synchrotron radiation measurements. The adsorption of elemental Se on Ta substrate at RT produces a film of Se multilayers. With subsequent heating up to 450 degrees C, the deposited Se interacts with Ta, leading to the formation of a TaSe2 thin film. The simultaneous co-adsorption of Se and TiCl4 on clean polycrystalline Ta at 250 degrees C produces a TiSe2 film of similar to 5 molecular layers. The production of TiSe2 film has been confirmed by Na intercalation and following de-intercalation of Na by exposure of the Na/TiSe2 film to TiCl4.