If the Ti cation is in a well-defined coordination environment, the degeneracy of the 3d-orbital final states is lifted due to the crystal field effect arising from hybridization with the occupied 2p orbitals of oxygen. This causes a splitting of the energy levels of the d orbitals. For octahedral complexes, the energies of the t2g inter-axial orbitals (dxz, dyz, dxy) decrease (become more stable) and the energy levels of the eg axial orbitals (dx2-dx2, dz2) increase, owing to the increased repulsion between electrons in the axial 3d orbitals and oxygen 2p. The Ti L2,3 edge arises largely from dipole-allowed transitions from the 2p1/2 and 2p3/2 occupied states into unoccupied 3d energy levels. L2,3 Crstal field splitting of the 3d-orbitals in octahedrally coordinated Ti 4+ results in a t2geg splitting of the unoccupied states and thus four peaks are observed in the L2,3-edge. For Ti 4+ cations, the characteristic doublets are well resolved, with clear separation between the t2g and eg peaks. In contrast, if Ti 3+ was present, the ionization threshold energy would shift to lower energy, and the four peaks are not clearly observed as a result of the multiplet effects . Our spatially resolved EELS data (Figure ) reveals that the t2g-eg crystal field splitting (Δ) is present through the outer, intermediate, and center perovskite layers, indicating an oxidation state of +4 for the Ti cation throughout the B6TFMO structure.