The effect of the inner particle structure on Li insertion activity and electronic structure of the nano-crystalline Li–Ti–O spinels was studied on materials prepared by solid state and solvothermal synthesis. The high temperature prepared materials of composition corresponding to Li4Ti5O12 feature particles with characteristic size of ca. 200nm with randomly distributed defects. The products of solvothermal synthesis with composition Li1.1Ti1.9O4+δ , feature cubic particles of characteristic dimension of ca. 50nm; the characteristic particle size differs from that of the coherent domain determined by X-ray diffraction. The reduction of the solvothermal and high temperature synthesized nano-crystalline spinels in Li containing solutions leads according to 6Li MAS NMR spectra to Li insertion into tetrahedral 8b and octahedral 16c position, respectively. Additional broad NMR signal attributable to a Knight shift was observed in spectra of partially reduced high temperature spinels. In the case of solvothermal spinels is the Knight shift signal less pronounced and appears only in spectra of samples in which the phase transition occurs on the local level. The UV–vis–NIR spectra of the partially reduced Li–Ti–O spinel samples correspond to expected semiconductor character of Li–Ti–O spinels. Both types of materials are characterized by band gap of 3.8eV (high temperature spinel) and 3.5eV (solvothermal material). Partial reduction accompanied with Li insertion causes additional optical transition in the visible to near infrared region, which can be attributed to formation of trivalent Ti, character of which changes with degree of reduction. The behavior observed for partially reduced high temperature spinels is similar to that reported for TiO2 (anatase). The spectral behavior of the partially reduced solvothermal spinels is more complex and reflects suppressed phase transition.