Changes in Ti K-edge X-ray absorption fine structure (XAFS) spectra of lithium titanium oxide (LTO) during the charge discharge cycle of lithium ion battery were investigated by using a specially designed cell for in situ X-ray measurement. Thought LTO is famous for zero-strain lattice during the charge/discharge cycle, the significant spectral changes might be attributed to Li migration in the lattice. The experimental results were compared with the theoretical simulation, and the spectral changes were caused both by the slight changes in oxygen position parameter that affected titanium neighbors and Li migration.