Spinel Li 4 Ti 5 O 12 has been considered as one of the most prospective anode materials for Li-ion microbatteries. Homogeneous, transparent and crack-free Li 4 Ti 5 O 12 coatings with thickness around 110 nm have been prepared by dipping gold-coated quartz substrates in sols prepared using titanium isopropoxide and lithium acetate. The influence of the thermal treatment on the phase composition, structure and electrochemical behavior was studied. Rutile TiO 2 (considered as an impurity in this study) is only detected in the coatings treated at 700 °C. XPS and TOF-SIMS depth profiles show a homogeneous distribution, with a Li increase and Ti reduction at the surface. Electrochemical characterization of samples treated at 600 °C presents a redox reaction around 1.55 V indicating that the film is simple phase of Li 4 Ti 5 O 12 . The shift to slightly lower voltage in samples treated at 700 °C is a consequence of Rutile impurities. Larger capacity and good reversibility in the sample heat-treated at 600 °C can be attributed to high crystallinity of Li 4 Ti 5 O 12 and phase purity. RBS analysis specifies a composition close to Li 4 Ti 5 O 12 in the case of the pristine and charged samples, and Li 7 Ti 5 O 12 for the discharged sample. Surface XPS study confirms the presence of an outermost layer containing LiF and Li 2 CO 3 .