The excitation and ionizationspectra of TiCl4 have been studied theoretically by the symmetry adapted cluster (SAC)/SAC‐CI and multireference CI (MRD‐CI) methods. The calculated spectra show good agreement with the observed spectra. The present results indicate several new assignments for the excitation spectrum. The peaks below 8.0 eV are assigned to valence excitations and those at 9.35 and 10.04 eV are assigned to Rydberg‐type excitations within chlorine ligands. The ordering of the ionized states in the outer valence region is (1t 1)−1 < (3t 2)−1 < (1e)−1 < (2t 2)−1 < (2a 1)−1, which supports the result of earlier Green’s function calculations.