Electron states of 1:2 addition compounds of TiCl4 with diethyl ether and diethyl sulfide in the vapor phase have been studied by HeI photoelectron (UVPES) and electron energy loss spectroscopies (EELS). The peaks in the photoelectron spectra of the complexes are assigned by comparison with the orbital energies from ab initio MO calculations on model compounds TiCl4-2(CH3)(2)O and TiCl4-2(CH3)(2)S. Lone pair orbitals of chlorine are shifted to lower binding energy by 1.6 eV; the pi type oxygen lone pair is shifted to higher binding energy by 1.8 eV and the sigma type lone pair of oxygen by 2.4 eV in the TiCl4-2(C2H5)(2)O complex. The magnitude of shifts in the Cl and S lone pairs in the TiCl4-(C2H5)(2)S are lower than that in the diethyl ether complex. Electronic excitation in TiCl4 and TiCl4-2(C2H5)(2)O are obtained by electron energy loss spectroscopy. A band at 3.6 eV observed in the case of the TiCl4-2(C2H5)(2)O complex molecule is assigned to the Cl(3p) ligand to Ti4+(3d) charge transfer. An energy level diagram of the TiCl4-2(C2H5)(2)O was drawn from the UVPES and EELS results describing the electronic transitions in the complex molecule.