The electronic structures of V-intercalated TiSe and substitutionally doped dichalcogenides TiVSe have been studied using soft X-ray photoelectron, resonant photoelectron, and absorption spectroscopies. In the case of the substitution of Ti by V, the formation of coherently oriented structural fragments VSe and TiSe is observed and a small charge transfer between these fragments is found. Intercalation of the V atoms into TiSe leads to charge transfer from the V atoms to the Ti atoms with the formation of covalent complexes Ti-Se-V-Se-Ti.
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