Resonant valence band x-ray photoelectron spectra (ResPES) excited near the 2p3/2 core level energies, 2p x-ray photoelectron spectra (XPS) and L3,2 x-ray absorption spectra (XAS) of Ti and Mn in single crystals of 1T-Mn0.2TiSe2 were studied for the first time. The ionic–covalent character of the bonds formed by the Mn atoms with the neighboring Se atoms in the octahedral coordination is established. From the XPS and XAS measurements compared with the results of atomic multiplet calculations of Ti and Mn L3,2 XAS, it is found that the Ti atoms are in the ionic state of 4 + and the Mn atoms are in the state of 2 + . In ResPES of Mn0.2TiSe2 excited near the Ti 2p3/2 and Mn 2p3/2 absorption edges the Ti 3d and Mn 3d bands at binding energies just below the Fermi level are observed. According to theoretical calculations of E(k) the Ti 3d states are localized in the vicinity of the Γ point and the Mn 3d states are localized along the direction K–Γ–M in the Brillouin zone of the crystal.