We report on a PE study of the electronic structure of pristine TiSe2. The experimental data are compared with results of band-structure calculations. It is confirmed that TiSe2 reveals semimetallic properties. For the first time rare-earth metals were attempted to be incorporated in situ into TiSe2. It is found that divalent Eu can be easy intercalated, whereas deposition of trivalent Gd leads to strong interfacial reactions. The electronic structure of the Eu-intercalation compound cannot be simply described within a rigid-band approach assuming charge transfer from Eu to unoccupied Ti d stares. In a more elaborated approach hybridization phenomena have to be taken into consideration.