Lithium titanate with spinel structure (Li4Ti5O12) has attracted attention for its potential use as anode in lithium-ion batteries. Usually, this material is obtained by solid-state reaction using high temperatures and considerable time in the calcination. Lithium titanate was synthesized in this study using a new approach of the oxidant peroxo method (OPM). The pure spinel phase was obtained by solid-state reaction utilizing commercial LiOH and TiO2 nanoparticles with surface modified with peroxo-groups (TiO2-OPM). These nanoparticles were synthesized from the peroxo-complex of titanium, formed on the OPM route. The results show that the use of TiO2-OPM as precursor favored the production of Li4Ti5O12 at lower temperature and time when compared to commercial titanium dioxide (TiO2-COM). The greater reactivity of this powder is related to the peroxo-groups present on the surface of the TiO2, since their decomposition generates a great amount of energy that accelerates the reaction.