Polarization-dependent Ti K X-ray absorption and Ti K α X-ray emission spectroscopy (XAS and XES) experiments have been carried out for single-crystalline Ti 2 O 3 with metal-insulator transition (MIT) around 450K. Both the XAS and XES spectra exhibit remarkable polarization dependences between E//c and E⊥c conditions, where the c-axis is parallel to the Ti ion pair direction and E represents a polarization vector of incident photons. The main peak of the E//c-XAS spectrum is 3eV lower in energy than the E⊥c-spectrum at 300K, reflecting the highly anisotropic unoccupied Ti 4p states, and the energy separation of the main peaks decreases to 2eV at 520K, in consistent with the reduced anisotropy of electronic structure followed by MIT. The broad features of the Ti K α XES spectra taken far below the Ti K absorption edge are similar to the XAS features including the polarization dependence, suggesting that the 2p4p monopole excitation causes the broad XES features, where 2p denotes a 2p core hole.